Structurally-colored articles and methods for making and using structurally-colored articles

ABSTRACT

As described above, one or more aspects of the present disclosure provide articles having structural color, and methods of making articles having structural color. The articles incorporate a primer layer having a percent transmittance of about 40% or less in conjunction with an optical element. The optical element and primer layer impart a structural color to the article.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of and priority to U.S. ProvisionalApplication Ser. No. 62/565,299, having the title “STRUCTURALLY COLOREDARTICLES AND METHODS OF MAKING STRUCTURALLY COLORED ARTICLES”, filed onSep. 29, 2017, and to U.S. Provisional Application Ser. No. 62/633,666,having the title “ARTICLES HAVING STRUCTURAL COLOR AND METHODS ANDSYSTEMS FOR MAKING ARTICLES HAVING STRUCTURAL COLOR”, filed on Feb. 22,2018, and to U.S. Provisional Application Ser. No. 62/565,306, havingthe title “STRUCTURALLY COLORED STRUCTURES AND ARTICLES, METHODS OFMAKING STRUCTURES AND ARTICLES”, filed on Sep. 29, 2017, and to U.S.Provisional Application Ser. No. 62/565,313, having the title“STRUCTURES HAVING STRUCTURAL COLOR AND METHODS AND SYSTEMS FOR MAKINGSTRUCTURES HAVING STRUCTURAL COLOR”, filed on Sep. 29, 2017, and U.S.Provisional Application Ser. No. 62/565,310, having the title“STRUCTURES HAVING STRUCTURAL COLOR AND METHODS AND SYSTEMS FOR MAKINGSTRUCTURES HAVING STRUCTURAL COLOR”, filed on Sep. 29, 2017, thedisclosures which are incorporated herein by reference in theirentireties.

BACKGROUND

Structural color is caused by the physical interaction of light with themicro- or nano-features of a surface and the bulk material as comparedto color derived from the presence of dyes or pigments that absorb orreflect specific wavelengths of light based on the chemical propertiesof the dyes or pigments. Color from dyes and pigments can be problematicin a number of ways. For example, dyes and pigments and their associatedchemistries for fabrication and incorporation into finished goods maynot be environmentally friendly.

BRIEF DESCRIPTION OF THE DRAWINGS

Further embodiments of the present disclosure will be more readilyappreciated upon review of the detailed description of its variousembodiments, described below, when taken in conjunction with theaccompanying drawings.

FIGS. 1A-1M shows various articles of footwear, apparel, athleticequipment, container, electronic equipment, and vision wear that includethe primer layer in accordance with the present disclosure.

FIGS. 2A-2B illustrate side views of exemplary optical elements of thepresent disclosure.

The drawings described herein are for illustration purposes only and arenot intended to limit the scope of the present disclosure in any way.

DESCRIPTION

The present disclosure provides for articles that exhibit structuralcolors through the use of a primer layer and an optical element, wherestructural colors are visible colors produced, at least in part, throughoptical effects (e.g., through scattering, refraction, reflection,interference, and/or diffraction of visible wavelengths of light Thearticle includes the primer layer, an optional textured surface, and theoptical element (e.g., a multilayer reflector or a multilayer filter),where the optical element is disposed on the a surface of the articlewith the optional textured surface and the primer layer between theoptical element and the surface, depending upon the design. Thecombination of the primer layer, the optional textured surface, and theoptical element imparts structural color (e.g., single color,multicolor, iridescent), to the article, where the structural color canbe designed to be different than the primer color, optionally with orwithout the application of pigments or dyes to the article. Thestructural color imparts an aesthetically appealing color to the articlewithout requiring the use of inks or pigments and the environmentalimpact associated with their use. The article can be a finished articlesuch as, for example, an article of footwear, apparel or sportingequipment. The article can be a component of an article of footwear,apparel or sporting equipment, such as, for example, an upper or a solefor an article of footwear, a waistband or arm or hood of an article ofapparel, a brim of a hat, a portion of a backpack, or a panel of asoccer ball, and the like.

The primer layer and the optical element can be used alone or optionallyin combination with the textured surface to impart the structural color.The textured surface and/or the primer layer can be part of the opticalelement or can be separate from the optical element, but, when used withthe optical element, impart the structural color. In other words, whilethe optical element and the primer layer alone can impart a firststructural color, the combination of the optical element and the primerlayer with the textured surface can impart a second structural color. Insome examples, the first structural color is the same as the secondstructural color. Alternatively, the second structural color can differfrom the first structural color based on a color parameter such as hue,lightness, or iridescence type. In such cases, the combination of theoptical element, the primer layer, and the optional textured surfaceimpart the structural color to the article.

After disposing the primer layer and the optical element onto thearticle, the article exhibits a different color from the underlyingsurface of the article, without the application of additional pigmentsor dyes to the article. For example, the structural color can differfrom the color of the underlying surface of the article based on a colorparameter such as hue, lightness, iridescence type, or any combinationthereof. In particular examples, the structural color and the color ofthe underlying surface of the article differ both in hue and iridescencetype, where the structural color is iridescent (e.g., exhibits two ormore different hues when viewed from at least two different angles 15degrees apart), and the color of the underlying surface is notiridescent.

The primer layer and the optical element can be disposed (e.g., affixed,attached, adhered, bonded, joined) on a surface of one or morecomponents of the footwear, such as on the shoe upper and/or the sole.The optical element can be incorporated into the sole by incorporatingit into a cushioning element such as a bladder or a foam. The soleand/or upper can be designed so that one or more portions of thestructurally colored component are visible in the finished article, byincluding an opening, or a transparent component covering thestructurally colored component, and the like.

An embodiment of the present disclosure provides for a method,comprising: disposing a primer layer having a percent transmittance ofabout 40% or less; and disposing an optical element on a top surface ofthe primer layer, wherein the primer layer, and the optical elementimpart a structural color. In addition, the method provides for anarticle comprising: a product of the method as described above orherein.

An embodiment of the present disclosure provides for a structurecomprising: a primer layer having a percent transmittance of 40 percentor less and an optical element, wherein the primer layer, and theoptical element impart the structural color.

While in many examples of this disclosure, a highly iridescentstructural color (e.g., a color which shifts over a wide range of hueswhen viewed from different angles) can be obtained, in other examples astructural color which does not shift over a wide range of hues whenviewed from different angles (e.g., a structural color which does notshift hues, or which shifts over a limited number of hues depending uponthe viewing angle) also can be obtained.

In one example, the present disclosure provides for the optical element,as disposed on an article, when measured according to the CIE 1976 colorspace under a given illumination condition at three observation anglesbetween −15 degrees and +60 degrees, has a first color measurement at afirst angle of observation having coordinates L₁* and a₁* and b₁*, and asecond color measurement at a second angle of observation havingcoordinates L₂* and a₂* and b₂*, and a third color measurement at athird angle of observation having coordinates L₃* and a₃* and b₃*,wherein the L₁*, L₂*, and L₃* values may be the same or different,wherein the a₁*, a₂*, and a₃* coordinate values may be the same ordifferent, wherein the b₁*, b₂*, and b₃* coordinate values may be thesame or different, and wherein the range of the combined a₁*, a₂* anda₃* values is less than about 40% of the overall scale of possible a*values.

In another example, the present disclosure provides for the opticalelement, as disposed on an article, when measured according to the CIE1976 color space under a given illumination condition at two observationangles between −15 degrees and +60 degrees, has a first colormeasurement at a first angle of observation having coordinates L₁* anda₁* and b₁*, and a second color measurement at a second angle ofobservation having coordinates L₂* and a₂* and b₂*, wherein the L₁* andL₂* values may be the same or different, wherein the a₁* and a₂*coordinate values may be the same or different, wherein the b₁* and b₂*coordinate values may be the same or different, and wherein the ΔE*_(ab)between the first color measurement and the second color measurement isless than or equal to about 100, whereΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)+(b₁*−b₂*)²]^(1/2).

In yet another example, the present disclosure provides for the opticalelement, as disposed on an article, when measured according to theCIELCH color space under a given illumination condition at threeobservation angles between −15 degrees and +60 degrees, has a firstcolor measurement at a first angle of observation having coordinates L₁*and C₁* and h₁°, and a second color measurement at a second angle ofobservation having coordinates L₂* and C₂* and h₂°, and a third colormeasurement at a third angle of observation having coordinates L₃* andC₃* and h₃°, wherein the L₁*, L₂*, and L₃* values may be the same ordifferent, wherein the C₁*, C₂*, and C₃* coordinate values may be thesame or different, wherein the h₁°, h₂° and h₃° coordinate values may bethe same or different, and wherein the range of the combined h₁°, h₂°and h₃° values is less than about 60 degrees.

Now having described embodiments of the present disclosure generally,additional discussion regarding embodiments will be described in greaterdetails.

This disclosure is not limited to particular embodiments described, andas such may, of course, vary. The terminology used herein serves thepurpose of describing particular embodiments only, and is not intendedto be limiting, since the scope of the present disclosure will belimited only by the appended claims.

Where a range of values is provided, each intervening value, to thetenth of the unit of the lower limit unless the context clearly dictatesotherwise, between the upper and lower limit of that range and any otherstated or intervening value in that stated range, is encompassed withinthe disclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges and are also encompassedwithin the disclosure, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded in the disclosure.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentdisclosure. Any recited method may be carried out in the order of eventsrecited or in any other order that is logically possible.

Embodiments of the present disclosure will employ, unless otherwiseindicated, techniques of material science, chemistry, textiles, polymerchemistry, and the like, which are within the skill of the art. Suchtechniques are explained fully in the literature.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art of material science, chemistry, textiles, polymer chemistry, andthe like. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentdisclosure, suitable methods and materials are described herein.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” may include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a support”includes a plurality of supports. In this specification and in theclaims that follow, reference will be made to a number of terms thatshall be defined to have the following meanings unless a contraryintention is apparent.

The present disclosure provides for articles that exhibit structuralcolor. The structural color can be imparted by the primer layer and theoptical element, incorporated onto one or more components of thearticle, for example, when the article is an article of footwear, on anupper or sole of an article of footwear. In one or more embodiments ofthe present disclosure the surface of the article includes the primerlayer, and the optical element (e.g., a signal layer, a multilayerreflector or a multilayer filter), and optionally a textured surface,where the primer layer, optical element, and optionally the texturedsurface impart structural color (e.g., single color, multicolor,iridescent). The primer layer has a percent transmittance of 40 percentor less. The optional textured surface and the primer layer can bedisposed between the optical element and the surface, depending upon thedesign. The structural color can be the same as or different than thecolor of the primer layer. In embodiments, the primer layer can beincluded in the optical element (e.g, single layer or multilayerstructures) or can be separate from the optical element, while stillbeing used to impart structural color.

The surface of the article can have one of the following structures:texture layer/primer layer/optical element or primer layer/texturelayer/optical element. The primer layer can have a thickness of about 3nanometers to 200 micrometers. In an aspect, the design used to impartthe structural color can include the combination of the primer layer,the optional textured surface and the optical element. Selection ofvariables associated with the primer layer, the optional, texture layer,and the optical element, can be used to control and select the desiredstructural color.

The primer layer can include a paint layer, a reground layer, an inklayer, and at least partially degraded polymer layer, a metal layer, anoxide layer, or a combination thereof. In an embodiment the primer layercan have a dark color. For example the dark color can be selected from:black, shades of black, brown, dark shades of brown, dark shades of red,dark shades of orange, dark shades of yellow, dark shades of green, darkshades of cyan, dark shades of blue, dark shades of violet, grey, darkshades of gray, dark shades of magenta, dark shades of indigo, tones,tints, shades, or hues of any of these, and a combination thereof.Additional details regarding the color are provided herein.

In an embodiment, the structural color is not used in combination with apigment and/or dye. In another aspect, the structural color is used incombination with a pigment and/or dye, but the structural color is notthe same color, shade, and/or hue as the pigment and/or dye. In thisregard, the structural color is the product of the primer layer, thetextured surface, the optical element, and the pigment and/or dye.

In an embodiment, the structural color is used in combination with apigment and/or dye to enhance the color of the pigment and/or dye inregard to the color of the pigment and/or dye or enhance a tone, tint,shade, or hue associated with the pigment and/or dye. The primer layercan include a red pigment and/or dye. The primer layer can include a redpigment and/or dye. The primer layer can include a black pigment and/ordye. The primer layer can include a black pigment and/or dye.

The article can be an article of manufacture or a component of thearticle. The article of manufacture can include footwear, apparel (e.g.,shirts, jerseys, pants, shorts, gloves, glasses, socks, hats, caps,jackets, undergarments), containers (e.g., backpacks, bags), andupholstery for furniture (e.g., chairs, couches, car seats), bedcoverings (e.g., sheets, blankets), table coverings, towels, flags,tents, sails, and parachutes, or components of any one of these. Inaddition, the primer layer can be used with or disposed on textiles orother items such as striking devices (e.g., bats, rackets, sticks,mallets, golf clubs, paddles, etc.), athletic equipment (e.g., golfbags, baseball and football gloves, soccer ball restriction structures),protective equipment (e.g., pads, helmets, guards, visors, masks,goggles, etc.), locomotive equipment (e.g., bicycles, motorcycles,skateboards, cars, trucks, boats, surfboards, skis, snowboards, etc.),balls or pucks for use in various sports, fishing or hunting equipment,furniture, electronic equipment, construction materials, eyewear,timepieces, jewelry, and the like.

The article can be an article of footwear. The article of footwear canbe designed for a variety of uses, such as sporting, athletic, military,work-related, recreational, or casual use. Primarily, the article offootwear is intended for outdoor use on unpaved surfaces (in part or inwhole), such as on a ground surface including one or more of grass,turf, gravel, sand, dirt, clay, mud, pavement, and the like, whether asan athletic performance surface or as a general outdoor surface.However, the article of footwear may also be desirable for indoorapplications, such as indoor sports including dirt playing surfaces forexample (e.g., indoor baseball fields with dirt infields).

In particular, the article of footwear can be designed for use in indooror outdoor sporting activities, such as global football/soccer, golf,American football, rugby, baseball, running, track and field, cycling(e.g., road cycling and mountain biking), and the like. The article offootwear can optionally include traction elements (e.g., lugs, cleats,studs, and spikes as well as tread patterns) to provide traction on softand slippery surfaces, where components of the present disclosure can beused or applied between or among the traction elements and optionally onthe sides of the traction elements but on the surface of the tractionelement that contacts the ground or surface. Cleats, studs and spikesare commonly included in footwear designed for use in sports such asglobal football/soccer, golf, American football, rugby, baseball, andthe like, which are frequently played on unpaved surfaces. Lugs and/orexaggerated tread patterns are commonly included in footwear includingboots design for use under rugged outdoor conditions, such as trailrunning, hiking, and military use.

In particular, the article can be an article of apparel (i.e., agarment). The article of apparel can be an article of apparel designedfor athletic or leisure activities. The article of apparel can be aarticle of apparel designed to provide protection from the elements(e.g., wind and/or rain), or from impacts.

In particular, the article can be an article of sporting equipment. Thearticle of sporting equipment can be designed for use in indoor oroutdoor sporting activities, such as global football/soccer, golf,American football, rugby, baseball, running, track and field, cycling(e.g., road cycling and mountain biking), and the like.

FIGS. 1A-1M illustrates footwear, apparel, athletic equipment,container, electronic equipment, and vision wear that include thestructure (e.g., including the primer layer, the optical element,optionally the textured surface) of the present disclosure. Thestructure is represented by hashed areas 12A′/12M′-12A″/12M′. Thelocation of the structure is provided only to indicate one possible areathat the structure can be located. Also, two locations are illustratedin some of the figures and one location is illustrated in other figures,but this is done only for illustration purposes as the items can includeone or a plurality of structure, where the size and location can bedetermined based on the item. The structure(s) located on each item canrepresent a number, letter, symbol, design, emblem, graphic mark, icon,logo, or the like.

Now have described embodiments of the present disclosure generally,additional details are provided. As has been described herein, thestructural color can include one of a number of colors. The “color” ofthe article as perceived by a viewer can differ from the actual color ofthe article, as the color perceived by a viewer is determined by theactual color of the article by the presence of optical elements whichmay absorb, refract, interfere with, or otherwise alter light reflectedby the article, by the viewer's ability to detect the wavelengths oflight reflected by the article, by the wavelengths of light used toilluminate the article, as well as other factors such as the colorationof the environment of the article, and the type of incident light (e.g.,sunlight, fluorescent light, and the like). As a result, the color of anobject as perceived by a viewer can differ from the actual color of thearticle.

Conventionally, color is imparted to man-made objects by applyingcolored pigments or dyes to the object. More recently, methods ofimparting “structural color” to man-made objects have been developed.Structural color is color which is produced, at least in part, bymicroscopically structured surfaces that interfere with visible lightcontacting the surface. The structural color is color caused by physicalphenomena including the scattering, refraction, reflection,interference, and/or diffraction of light, unlike color caused by theabsorption or emission of visible light through coloring matters. Forexample, optical phenomena which impart structural color can includemultilayer interference, thin-film interference, refraction, dispersion,light scattering, Mie scattering, diffraction, and diffraction grating.In various aspects described herein, structural color imparted to anarticle can be visible to a viewer having 20/20 visual acuity and normalcolor vision from a distance of about 1 meter from the article.

As described herein, structural color is produced, at least in part, bythe optical element, as opposed to the color being produced solely bypigments and/or dyes. The coloration of a structurally-colored articlecan be due solely to structural color (i.e., the article, a coloredportion of the article, or a colored outer layer of the article can besubstantially free of pigments and/or dyes). Structural color can alsobe used in combination with pigments and/or dyes, for example, to alterall or a portion of a structural color.

“Hue” is commonly used to describe the property of color which isdiscernible based on a dominant wavelength of visible light, and isoften described using terms such as magenta, red, orange, yellow, green,cyan, blue, indigo, violet, etc. or can be described in relation (e.g.,as similar or dissimilar) to one of these. The hue of a color isgenerally considered to be independent of the intensity or lightness ofthe color. For example, in the Munsell color system, the properties ofcolor include hue, value (lightness) and chroma (color purity).Particular hues are commonly associated with particular ranges ofwavelengths in the visible spectrum: wavelengths in the range of about700 to 635 nanometers are associated with red, the range of about 635 to590 nanometers is associated with orange, the range of about 590 to 560nanometers is associated with yellow, the range of about 560 to 520nanometers is associated with green, the range of about 520 to 490nanometers is associated with cyan, the range of about 490 nanometers to450 nanometers is associated with blue, and the range of about 450 to400 nanometers is associated with violet.

The color (including the hue) of an article as perceived by a viewer candiffer from the actual color of the article. The color as perceived by aviewer depends not only on the physics of the article, but also itsenvironment, and the characteristics of the perceiving eye and brain.For example, as the color perceived by a viewer is determined by theactual color of the article (e.g., the color of the light leaving thesurface of the article), by the viewer's ability to detect thewavelengths of light reflected or emitted by the article, by thewavelengths of light used to illuminate the article, as well as otherfactors such as the coloration of the environment of the article, andthe type of incident light (e.g., sunlight, fluorescent light, and thelike). As a result, the color of an object as perceived by a viewer candiffer from the actual color of the article.

When used in the context of structural color, one can characterize thehue of a structurally-colored article, i.e., an article that has beenstructurally colored by incorporating an optical element into thearticle, based on the wavelengths of light the structurally-coloredportion of the article absorbs and reflects (e.g., linearly andnon-linearly). While the optical element may impart a first structuralcolor, the presence of an optional textured surface and/or primer layercan alter the structural color. Other factors such as coatings ortransparent elements may further alter the perceived structural color.The hue of the structurally colored article can include any of the huesdescribed herein as well as any other hues or combination of hues. Thestructural color can be referred to as a “single hue” (i.e., the hueremains substantially the same, regardless of the angle of observationand/or illumination), or “multihued” (i.e., the hue varies dependingupon the angle of observation and/or illumination). The multihuedstructural color can be iridescent (i.e., the hue changes gradually overtwo or more hues as the angle of observation or illumination changes).The hue of an iridescent multihued structural color can change graduallyacross all the hues in the visible spectrum (e.g., like a “rainbow”) asthe angle of observation or illumination changes. The hue of aniridescent multihued structural color can change gradually across alimited number of hues in the visible spectrum as the angle ofobservation or illumination changes, in other words, one or more hues inthe visible spectrum (e.g., red, orange, yellow, etc.) are not observedin the structural color as the angle of observation or illuminationchanges. Only one hue, or substantially one hue, in the visible spectrummay be present for a single-hued structural color. The hue of amultihued structural color can change more abruptly between a limitednumber of hues (e.g., between 2-8 hues, or between 2-4 hues, or between2 hues) as the angle of observation or illumination changes.

The structural color can be a multi-hued structural color in which twoor more hues are imparted by the structural color.

The structural color can be iridescent multi-hued structural color inwhich the hue of the structural color varies over a wide number of hues(e.g., 4, 5, 6, 7, 8 or more hues) when viewed at a single viewingangle, or when viewed from two or more different viewing angles that areat least 15 degrees apart from each other.

The structural color can be limited iridescent multi-hue structuralcolor in which the hue of the structural color varies, or variessubstantially (e.g., about 90 percent, about 95 percent, or about 99percent) over a limited number of hues (e.g, 2 hues, or 3 hues) whenviewed from two or more different viewing angles that are at least 15degrees apart from each other. In some aspects, a structural colorhaving limited iridescence is limited to two, three or four huesselected from the RYB primary colors of red, yellow and blue, optionallythe RYB primary and secondary colors of red, yellow, blue, green, orangeand purple, or optionally the RYB primary, secondary and tertiary colorsof red, yellow, blue, green, orange purple, green-yellow, yellow-orange,orange-red, red-purple, purple-blue, and blue-green.

The structural color can be single-hue angle-independent structuralcolor in which the hue, the hue and value, or the hue, value and chromaof the structural color is independent of or substantially (e.g., about90 percent, about 95 percent, or about 99 percent) independent of theangle of observation. For example, the single-hue angle-independentstructural color can display the same hue or substantially the same huewhen viewed from at least 3 different angles that are at least 15degrees apart from each other (e.g., single-hue structural color).

The structural color imparted can be a structural color having limitediridescence such that, when each color observed at each possible angleof observation is assigned to a single hue selected from the groupconsisting of the primary, secondary and tertiary colors on the redyellow blue (RYB) color wheel, for a single structural color, all of theassigned hues fall into a single hue group, wherein the single hue groupis one of a) green-yellow, yellow, and yellow-orange; b) yellow,yellow-orange and orange; c) yellow-orange, orange, and orange-red; d)orange-red, and red-purple; e) red, red-purple, and purple; f)red-purple, purple, and purple-blue; g) purple, purple-blue, and blue;h) purple-blue, blue, and blue-green; i) blue, blue-green and green; andj) blue-green, green, and green-yellow. In other words, in this exampleof limited iridescence, the hue (or the hue and the value, or the hue,value and chroma) imparted by the structural color varies depending uponthe angle at which the structural color is observed, but the hues ofeach of the different colors viewed at the various angles ofobservations varies over a limited number of possible hues. The huevisible at each angle of observation can be assigned to a singleprimary, secondary or tertiary hue on the red yellow blue (RYB) colorwheel (i.e., the group of hues consisting of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green). For example, while a plurality ofdifferent colors are observed as the angle of observation is shifted,when each observed hue is classified as one of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green, the list of assigned hues includes no morethan one, two, or three hues selected from the list of RYB primary,secondary and tertiary hues. In some examples of limited iridescence,all of the assigned hues fall into a single hue group selected from huegroups a)-j), each of which include three adjacent hues on the RYBprimary, secondary and tertiary color wheel. For example, all of theassigned hues can be a single hue within hue group h) (e.g., blue), orsome of the assigned hues can represent two hues in hue group h) (e.g.,purple-blue and blue), or can represent three hues in hue group h)(e.g., purple-blue, blue, and blue-green).

Similarly, other properties of the structural color, such as thelightness of the color, the saturation of the color, and the purity ofthe color, among others, can be substantially the same regardless of theangle of observation or illumination, or can vary depending upon theangle of observation or illumination. The structural color can have amatte appearance, a glossy appearance, or a metallic appearance, or acombination thereof.

As discussed above, the color (including hue) of a structurally-coloredarticle (e.g., an article include structural color) can vary dependingupon the angle at which the structurally-colored article is observed orilluminated. The hue or hues of an article can be determined byobserving the article, or illuminating the article, at a variety ofangles using constant lighting conditions. As used herein, the “angle”of illumination or viewing is the angle measured from an axis or planethat is orthogonal to the surface. The viewing or illuminating anglescan be set between about 0 and 180 degrees. The viewing or illuminatingangles can be set at 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60degrees, and −15 degrees and the color can be measured using acolorimeter or spectrophotometer (e.g., Konica Minolta), which focuseson a particular area of the article to measure the color. The viewing orilluminating angles can be set at 0 degrees, 15 degrees, 30 degrees, 45degrees, 60 degrees, 75 degrees, 90 degrees, 105 degrees, 120 degrees,135 degrees, 150 degrees, 165 degrees, 180 degrees, 195 degrees, 210degrees, 225 degrees, 240 degrees, 255 degrees, 270 degrees, 285degrees, 300 degrees, 315 degrees, 330 degrees, and 345 degrees and thecolor can be measured using a colorimeter or spectrophotometer. In aparticular example of a multihued article colored using only structuralcolor, when measured at 0 degrees, 15 degrees, 30 degrees, 45 degrees,60 degrees, and −15 degrees, the hues measured for article consisted of“blue” at three of the measurement angles, “blue-green” at 2 of themeasurement angles and “purple” at one of the measurement angles.

In other embodiments, the color (including hue, value and/or chroma) ofa structurally-colored article does not change substantially, if at all,depending upon the angle at which the article is observed orilluminated. In instances such as this the structural color can be anangle-independent structural color in that the hue, the hue and value,or the hue, value and chroma observed is substantially independent or isindependent of the angle of observation.

Various methodologies for defining color coordinate systems exist. Oneexample is L*a*b* color space, where, for a given illuminationcondition, L* is a value for lightness, and a* and b* are values forcolor-opponent dimensions based on the CIE coordinates (CIE 1976 colorspace or CIELAB). In an embodiment, a structurally-colored articlehaving structural color can be considered as having a “single” colorwhen the change in color measured for the article is within about 10% orwithin about 5% of the total scale of the a* or b* coordinate of theL*a*b* scale (CIE 1976 color space) at three or more measuredobservation or illumination angles selected from measured at observationor illumination angles of 0 degrees, 15 degrees, 30 degrees, 45 degrees,60 degrees, and −15 degrees. In certain embodiments, colors which, whenmeasured and assigned values in the L*a*b* system that differ by atleast 5 percent of the scale of the a* and b* coordinates, or by atleast 10 percent of the scale of the a* and b* coordinates, areconsidered to be different colors. The structurally-colored article canhave a change of less than about 40%, or less than about 30%, or lessthan about 20%, or less than about 10%, of the total scale of the a*coordinate or b* coordinate of the L*a*b* scale (CIE 1976 color space)at three or more measured observation or illumination angles.

A change in color between two measurements in the CIELAB space can bedetermined mathematically. For example, a first measurement hascoordinates L₁*, a₁* and b₁*, and a second measurement has coordinatesL₂*, a₂* and b₂*. The total difference between these two measurements onthe CIELAB scale can be expressed as ΔE*_(ab), which is calculated asfollows: ΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2). Generallyspeaking, if two colors have a ΔE*_(ab) of less than or equal to 1, thedifference in color is not perceptible to human eyes, and if two colorshave a ΔE*_(ab) of greater than 100 the colors are considered to beopposite colors, while a ΔE*_(ab) of about 2-3 is considered thethreshold for perceivable color difference. In certain embodiments, astructurally colored article having structural color can be consideredas having a “single” color when the ΔE*_(ab) is less than 60, or lessthan 50, or less than 40, or less than 30, between three or moremeasured observation or illumination angles selected from measured atobservation or illumination angles of 0 degrees, 15 degrees, 30 degrees,45 degrees, 60 degrees, and −15 degrees. The structurally-coloredarticle can have a ΔE*ab that is less than about 100, or less than about80, or less than about 60, between two or more measured observation orillumination angles.

Another example of a color scale is the CIELCH color space, where, for agiven illumination condition, L* is a value for lightness, C* is a valuefor chrome, and h° denotes a hue as an angular measurement. In anembodiment, a structurally-colored article having structural color canbe considered as having a “single” color when the color measured for thearticle is less than 10 degrees different or less than 5 degreesdifferent at the h° angular coordinate of the CIELCH color space, atthree or more measured observation or illumination angles selected frommeasured at observation or illumination angles of 0 degrees, 15 degrees,30 degrees, 45 degrees, 60 degrees, and −15 degrees. In certainembodiments, colors which, when measured and assigned values in theCIELCH system that vary by at least 45 degrees in the h° measurements,are considered to be different colors The structurally-colored articlecan have a change of less than about 60 degrees, or less than about 50degrees, or less than about 40 degrees, or less than about 30 degrees,or less than about 20 degrees, or less than about 10 degrees, in the h°measurements of the CIELCH system at three or more measured observationor illumination angles.

Another system for characterizing color includes the “PANTONE” MatchingSystem (Pantone LLC, Carlstadt, N.J., USA), which provides a visualcolor standard system to provide an accurate method for selecting,specifying, broadcasting, and matching colors through any medium. In anexample, a structurally-colored article having a structural color can beconsidered as having a “single” color when the color measured for thearticle is within a certain number of adjacent standards, e.g., within20 adjacent PANTONE standards, at three or more measured observation orillumination angles selected from 0 degrees, 15 degrees, 30 degrees, 45degrees, 60 degrees, and −15 degrees.

Now having described the color, additional details will be provided forthe primer layer. The optical element is used to produce the structuralcolor, where the optical element can include (e.g., as part of theoptical element) or use the primer layer to produce the structuralcolor. As described herein, the optical element can also include (e.g.,as part of optical element) the optional textured surface, such as atexture layer and/or a textured structure. The combination of theoptical element and the optional texture layer and the optional primerlayer can form a composite optical element (e.g., a component) havingone of the following structures: texture layer/primer layer/opticalelement or primer layer/texture layer/optical element. The primer layercan have a thickness of about 3 nanometers to 200 micrometers, or about1 to about 200 micrometers, or about 10 to about 100 micrometers, orabout 10 to about 80 micrometers. The composite optical element caninclude the combination of the primer layer, the optical element, and(optionally) textured surface. Selection of variables associated withthe primer layer, texture layer, and the optical element, can be used tocontrol and select the desired structural color.

The composite optical element can include the primer layer, the texturedsurface (optionally), and the optical element (e.g., optical layer),where the optical element is disposed on the textured surface or theprimer layer, depending upon the design. The combination of the primerlayer, the textured surface, and the optical element imparts structuralcolor, to the article, where the structural color is different than theprimer color, optionally with or without the application of pigments ordyes to the article. The optical element can be disposed onto the primerlayer and/or the textured surface. The primer layer can include thetextured surface as described herein. For example, the primer layer canbe formed in a way so that it has the textured surface.

The primer layer can include a paint layer (e.g., dyes, pigments, and acombination thereof), an ink layer, a reground layer, an at leastpartially degraded polymer layer, a metal layer, an oxide layer, or acombination thereof. The primer layer can have a light or dark color.The primer layer can have a dark color such as those described herein:black, shades of black, brown, dark shades of brown, dark shades of red,dark shades of orange, dark shades of yellow, dark shades of green, darkshades of cyan, dark shades of blue, dark shades of violet, grey, darkshades of gray, dark shades of magenta, dark shades of indigo, tones,tints, shades, or hues of any of these, and a combination thereof. Thecolor can be defined using the L*a*b system, where the value of L* canbe about 70 or less, about 60 or less, about 50 or less, about 40 orless, or about 30 or less and a* and b* coordinate values can varyacross the positive and negative value scales.

The primer layer can be formed using digital printing, inkjet printing,offset printing, pad printing, screen printing, flexographic printing,heat transfer printing, physical vapor deposition including: chemicalvapor deposition, pulsed laser deposition, evaporative deposition,sputtering deposition (radio frequency, direct current, reactive,non-reactive), plasma enhanced chemical vapor deposition, electron beamdeposition, cathodic arc deposition, low pressure chemical vapordeposition and wet chemistry techniques such as layer by layerdeposition, sol-gel deposition, or Langmuir blodgett. Alternatively orin addition, the primer layer can be applied by spray coating, dipcoating, brushing, spin coating, doctor blade coating, and the like.

The primer layer can have a percent transmittance of about 40% or less,about 30% or less, about 20% or less, about 15% or less, about 10% orless, about 5% or less, or about 1% or less, where “less” can includeabout 0% (e.g., 0 to 0.01 or 0 to 0.1), about 1%, about 2.5%, or about5%.

The primer layer can include a paint composition that, upon applying tothe article, forms a thin layer. The thin layer can be a solid filmhaving a dark color, such as those described above. The paintcomposition can include known paint compositions that can comprise oneor more of the following components: one or more paint resin, one ormore polymers, one or more dyes, and one or more pigments as well aswater, film-forming solvents, drying agents, thickeners, surfactants,anti-skinning agents, plasticizers, mildewcides, mar-resistant agents,anti-flooding agents, and combinations thereof.

The primer layer can comprise a reground, and at least partiallydegraded, polymer layer. The reground, and at least partially degraded,polymer layer can have a dark color, such as those described above.

The primer layer can include a metal layer or the oxide layer. The metallayer or the oxide layer can have a dark color, such as those describedabove. The oxide layer can be a metal oxide, a doped metal oxide, or acombination thereof. The metal layer, the metal oxide or the doped metaloxide can include the following: the transition metals, the metalloids,the lanthanides, and the actinides, as well as nitrides, oxynitrides,sulfides, sulfates, selenides, tellurides and a combination of these.The metal oxide can include titanium oxide, aluminum oxide, silicondioxide, tin dioxide, chromia, iron oxide, nickel oxide, silver oxide,cobalt oxide, zinc oxide, platinum oxide, palladium oxide, vanadiumoxide, molybdenum oxide, lead oxide, and combinations thereof as well asdoped versions of each. In some aspects, the primer layer can consistessentially of a metal oxide. In some aspects, the primer layer canconsist essentially of titanium dioxide or silicon dioxide. In someaspects, the primer layer can consist essentially of titanium dioxide.The metal oxide can be doped with water, inert gasses (e.g., argon),reactive gasses (e.g., oxygen or nitrogen), metals, small molecules, anda combination thereof. In some aspects, the primer layer can consistessentially of a doped metal oxide or a doped metal oxynitride or both.

The primer layer can be a coating on the surface of the article. Thecoating can be chemically bonded (e.g., covalently bonded, ionicallybonded, hydrogen bonded, and the like) to the surface of the article.The coating has been found to bond well to a surface made of a polymericmaterial. In an example, the surface of the article can be made of apolymeric material such as a polyurethane, including a thermoplasticpolyurethane (TPU), as those described herein.

The coating can be a crosslinked coating that includes one or morecolorants such as solid pigment particles or dye. The crosslinkedcoating can be a matrix of crosslinked polymers (e.g., a crosslinkedpolyester polyurethane polymer or copolymer). The colorants can beentrapped in the coating, including entrapped in the matrix ofcrosslinked polymers. The solid pigment particles or dye can bephysically entrapped in the crosslinked polymer matrix, can bechemically bonded (e.g., covalently bonded, ionically bonded, hydrogenbonded, and the like, with the coating including the polymeric matrix orwith the material forming the surface of the article to which thecoating is applied), or a combination of physically bonded andchemically bonded with the coating or article. The crosslinked coatingcan have a thickness of about 0.01 micrometers to 1000 micrometers.

The coating can be a product (or also referred to as “crosslinkedproduct”) of crosslinking a polymeric coating composition. The polymericcoating composition can include one or more colorants (e.g., solidpigment particles or dye) in a dispersion of polymers. The dispersion ofpolymers can include a water-borne dispersion of polymers such as awater-borne dispersion of polyurethane polymers, including polyesterpolyurethane copolymers). The water-borne dispersion of polymers can becrosslinked to entrap the colorants. The colorants can be physicallyentrapped in the crosslinked product, can be chemically bonded (e.g.,covalently bonded, ionically bonded, hydrogen bonded, and the like, withthe crosslinked copolymer matrix), or can be both physically bonded andchemically bonded with the crosslinked product. The product can beformed by crosslinking the polymeric coating composition. The productcan have a thickness of about 0.01 micrometer to 1000 micrometers.

The coating can include colorants such a pigment (e.g., a solid pigmentparticle) or a dye. The solid pigment particles can include inorganicpigments such as metal and metal oxides such as homogeneous inorganicpigments, core-shell pigments and the like, as well as carbon pigments(e.g., carbon black), clay earth pigments, and ultramarine pigments. Thesolid pigment particles can be biological or organic pigments. The solidpigment particles can be of a type known in the art as an extenderpigment, which include, but are not limited to, calcium carbonate,calcium silicate, mica, clay, silica, barium sulfate and the like. Theamount of the solid pigment particles sufficient to achieve the desiredcolor intensity, shade, and opacity, can be in amounts up to about 5percent to 25 percent or more by weight of the coating. The pigments caninclude those sold by KP Pigments such as pearl pigments, color shiftpigments (e.g., CALYPSO, JEDI, VERO, BLACKHOLE, LYNX, ROSE GOLD, and thelike), hypershift pigments, interference pigments and the like. Thecolorant can be a dye such as an anionic dye, a cationic dye, a directdye, a metal complex dye, a basic dye, a disperse dye, a solvent dye, apolymeric dye, a polymeric dye colorant, or a nonionic dye, where thecoating can include one or more dyes and/or types of dyes. The dye canbe a water-miscible dye. The dye can be a solubilized dye. The anionicdye can be an acid dye. The dye can be applied separately from thecoating (e.g., either before or after the coating is applied and/orcured).

Acid dyes are water-soluble anionic dyes. Acid dyes are available in awide variety, from dull tones to brilliant shades. Chemically, acid dyesinclude azo, anthraquinone and triarylmethane compounds. The “ColorIndex” (C.I.), published jointly by the Society of Dyers and Colourists(UK) and by the American Association of Textile Chemists and Colorists(USA), is the most extensive compendium of dyes and pigments for largescale coloration purposes, including 12000 products under 2000 C.I.generic names. In the C.I. each compound is presented with two numbersreferring to the coloristic and chemical classification. The “genericname” refers to the field of application and/or method of coloration,while the other number is the “constitution number.” Examples of aciddyes include Acid Yellow 1, 17, 23, 25, 34, 42, 44, 49, 61, 79, 99, 110,116, 127, 151, 158:1, 159, 166, 169, 194, 199, 204, 220, 232, 241, 246,and 250; Acid Red, 1, 14, 17, 18, 42, 57, 88, 97, 118, 119, 151, 183,184, 186, 194, 195, 198, 211, 225, 226, 249, 251, 257, 260, 266, 278,283, 315, 336, 337, 357, 359, 361, 362, 374, 405, 407, 414, 418, 419,and 447; Acid Violet 3, 5, 7, 17, 54, 90, and 92; Acid Brown 4, 14, 15,45, 50, 58, 75, 97, 98, 147, 160:1, 161, 165, 191, 235, 239, 248, 282,283, 289, 298, 322, 343, 349, 354, 355, 357, 365, 384, 392, 402, 414,420, 422, 425, 432, and 434; Acid Orange 3, 7, 10, 19, 33, 56, 60, 61,67, 74, 80, 86, 94, 139, 142, 144, 154, and 162; Acid Blue 1, 7, 9, 15,92, 133, 158, 185, 193, 277, 277:1, 314, 324, 335, and 342; Acid Green1, 12, 68:1, 73, 80, 104, 114, and 119; Acid Black 1, 26, 52, 58, 60,64, 65, 71, 82, 84, 107, 164, 172, 187, 194, 207, 210, 234, 235, andcombinations of these. The acid dyes may be used singly or in anycombination in the ink composition.

Acid dyes and nonionic disperse dyes are commercially available frommany sources, including Dystar L.P., Charlotte, N.C. under the tradenameTELON, Huntsman Corporation, Woodlands, Tex., USA under the tradenameERIONYL and TECTILON, BASF SE, Ludwigshafen, Germany under the tradenameBASACID, and Bezema AG, Montlingen, Switzerland under the tradenameBemacid.

The colorant can include the dye and a quaternary (tetraalkyl) ammoniumsalt, in particular when the dye is acidic dye. The quaternary(tetraalkyl) ammonium salt can react with the dye (e.g., acid dye) toform a complexed dye that can be used in the coating. The “alkyl” groupcan include C1 to C10 alkyl groups. The quaternary (tetraalkyl) ammoniumsalt can be selected from soluble tetrabutylammonium compounds andtetrahexylammonium compounds. The counterion of the quaternary ammoniumsalt should be selected so that the quaternary ammonium salt forms astable solution with the dye (e.g., anionic dye). The quaternaryammonium compound may be, for example, a halide (such as chloride,bromide or iodide), hydroxide, sulfate, sulfite, carbonate, perchlorate,chlorate, bromate, iodate, nitrate, nitrite, phosphate, phosphite,hexfluorophosphite, borate, tetrafluoroborate, cyanide, isocyanide,azide, thiosulfate, thiocyanate, or carboxylate (such as acetate oroxalate). The tetraalkylammonium compound can be or include atetrabutylammonium halide or tetrahexylammonium halide, particularly atetrabutylammonium bromide or chloride or a tetrahexylammonium bromideor chloride. The coating (e.g., coating, polymeric coating composition(prior to curing) can include about 1 to 15 weight percent of thequaternary ammonium salt. The molar ratio of the acid dye to thequaternary ammonium compound can range from about 3:1 to 1:3 or about1.5:1 to 1:1.5.

The coating (e.g., coating, polymeric coating composition (prior tocuring), monomers and/or polymers of the matrix of crosslinked polymers,or precursors of the coating) can include a cross-linker, whichfunctions to crosslink the polymeric components of the coating. Thecross-linker can be a water-borne cross-linker. The cross-linker caninclude one or more of the following: a polycarboxylic acid crosslinkingagent, an aldehyde crosslinking agent, a polyisocyanate crosslinkingagent, or a combination thereof. The polycarboxylic acid crosslinkingagent can be a polycarboxylic acid having from 2 to 9 carbon atoms. Forexample, the cross-linker can include a polyacrylic acid, a polymaleicacid, a copolymer of acid, a copolymer of maleic acid, fumaric acid, or1,2,3,4-butanetetracarboxylic acid. The concentration of thecross-linker can be about 0.01 to 5 weight percent or 1 to 3 weightpercent of the coating.

The coating (e.g., coating, polymeric coating composition (prior tocuring), monomers and/or polymers of the matrix of crosslinked polymers,or precursors of the coating) can include a solvent. The solvent can bean organic solvent. The organic solvent can be a water-miscible organicsolvent. The coating may not include water, or may be essentially freeof water. For example, the solvent can be or includes acetone, ethanol,2-propanol, ethyl acetate, isopropyl acetate, methanol, methyl ethylketone, 1-butanol, t-butanol, or any mixture thereof.

Now having described color and the primer layer, additional detailsregarding the optical element are provided. As described herein, thearticle includes the optical element. The optical element includes atleast one optical layer. The optical element that can be or include asingle or multilayer reflector or a multilayer filter. The opticalelement can function to modify the light that impinges thereupon so thatstructural color is imparted to the article. The optical element caninclude at least one optical layer and optionally one or more additionallayers (e.g., a protective layer, the textured layer, the primer layer,a polymer layer, and the like).

The method of making the structurally colored article can includedisposing (e.g., affixing, attaching, bonding, fastening, joining,appending, connecting, binding) the optical element onto an article(e.g., an article of footwear, an article of apparel, an article ofsporting equipment, etc.). The article includes a component, and thecomponent has a surface upon which the optical element can be disposed.The surface of the article can be made of a material such as athermoplastic material or thermoset material, as described herein. Forexample, the article has a surface including a thermoplastic material(i.e., a first thermoplastic material), for example an externally-facingsurface of the component or an internally-facing surface of thecomponent (e.g., an externally-facing surface or an internally-facingsurface a bladder). The optical element can be disposed onto thethermoplastic material, for example.

In an aspect, the temperature of at least a portion of the first surfaceof the article including the thermoplastic material is increased to atemperature at or above creep relaxation temperature (Tcr), Vicatsoftening temperature (Tvs), heat deflection temperature (Thd), and/ormelting temperature (Tm) of the thermoplastic material, for example tosoften or melt the thermoplastic material. The temperature can beincreased to a temperature at or above the creep relaxation temperature.The temperature can be increased to a temperature at or above the Vicatsoftening temperature. The temperature can be increased to a temperatureat or above the heat deflection temperature. The temperature can beincreased to a temperature at or above the melting temperature. Whilethe temperature of the at least a portion of the first side of thearticle is at or above the increased temperature (e.g., at or above thecreep relaxation temperature, the heat deflection temperature, the Vicatsoftening temperature, or the melting temperature of the thermoplasticmaterial), the optical element is affixed to the thermoplastic materialwithin the at least a portion of the first side of the article.Following the affixing, the temperature of the thermoplastic material isdecreased to a temperature below its creep relaxation temperature to atleast partially re-solidify the thermoplastic material. Thethermoplastic material can be actively cooled (e.g., removing the sourcethat increases the temperature and actively (e.g., flowing cooler gasadjacent the article reducing the temperature of the thermoplasticmaterial) or passively cooled (e.g., removing the source that increasesthe temperature and allowing the thermoplastic layer to cool on itsown).

The method of making the structurally-colored article can includedisposing (e.g., affixing, attaching, bonding, fastening, joining,appending, connecting, binding, which includes operably disposing etc.)the optical element onto a surface of an article (e.g., an article offootwear, an article of apparel, an article of sporting equipment, etc.)or a surface of a component of an article. The article can include acomponent, and the component can include the surface upon which theoptical element is be disposed. The surface of the article can be madeof a material such as a thermoplastic material or thermoset material, asdescribed herein. For example, the article can have a surface includinga thermoplastic material (i.e., a first thermoplastic material), forexample an externally-facing surface of the component or article or aninternally-facing surface of the component or article (e.g., anexternally-facing surface or an internally-facing surface a bladder).The optical element can be disposed onto the thermoplastic material, forexample.

The optical element has a first side (including the outer surface) and asecond side opposing the first side (including the opposing outersurface), where the first side or the second side is adjacent thearticle. For example, when the optical element is used in conjunctionwith a component having internally-facing and externally-facingsurfaces, such as a film or a bladder, the first side of the opticalelement can be disposed on the internally-facing surface of thecomponent, such as in the following order: second side of the opticalelement/core of the optical element/first side of the opticalelement/internally-facing surface of the component/core of thecomponent/externally-facing surface of the component. Alternatively, thesecond side the optical element can be disposed on the internally-facingsurface of the component, such as in the following order: first side ofthe optical element/core of the optical element/second side of theoptical element/internally-facing surface of the component/core of thecomponent wall/externally-facing surface of the component. In anotherexample, the first side of the optical element can be disposed on theexternally-facing surface of the component, such as in the followingorder: internally-facing surface of the component/core of thecomponent/externally-facing surface of the component/first side of theoptical element/core of the optical element/second side of the opticalelement. Similarly, the second side of the optical element can bedisposed on the externally-facing surface of the component, such as inthe following order: internally-facing surface of the component/core ofthe component/externally-facing surface of the component/second side ofthe optical element/core of the optical element/first side of theoptical element. In examples where the optional textured surface, theoptional primer layer, or both are present, the textured surface and/orthe primer layer can be located at the interface between the surface ofthe component and a side of the optical element.

The optical element or layers or portions thereof (e.g., optical layer)can be formed using known techniques such as physical vapor deposition,electron beam deposition, atomic layer deposition, molecular beamepitaxy, cathodic arc deposition, pulsed laser deposition, sputteringdeposition (e.g., radio frequency, direct current, reactive,non-reactive), chemical vapor deposition, plasma-enhanced chemical vapordeposition, low pressure chemical vapor deposition and wet chemistrytechniques such as layer-by-layer deposition, sol-gel deposition,Langmuir blodgett, and the like. The temperature of the first side canbe adjusted using the technique to form the optical element and/or aseparate system to adjust the temperature. Additional details areprovided herein.

The optical layer(s) of the optical element can comprise a multilayerreflector. The multilayer reflector can be configured to have a certainreflectivity at a given wavelength of light (or range of wavelengths)depending, at least in part, on the material selection, thickness andnumber of the layers of the multilayer reflector. In other words, onecan carefully select the materials, thicknesses, and numbers of thelayers of a multilayer reflector and optionally its interaction with oneor more other layers, so that it can reflect a certain wavelength oflight (or range of wavelengths), to produce a desired structural color.The optical layer can include at least two adjacent layers, where theadjacent layers have different refractive indices. The difference in theindex of refraction of adjacent layers of the optical layer can be about0.0001 to 50 percent, about 0.1 to 40 percent, about 0.1 to 30 percent,about 0.1 to 20 percent, about 0.1 to 10 percent (and other ranges therebetween (e.g., the ranges can be in increments of 0.0001 to 5 percent)).The index of refraction depends at least in part upon the material ofthe optical layer and can range from 1.3 to 2.6.

The optical layer can include 2 to 20 layers, 2 to 10 layer, 2 to 6layers, or 2 to 4 layers. Each layer of the optical layer can have athickness that is about one-fourth of the wavelength of light to bereflected to produce the desired structural color. Each layer of theoptical layer can have a thickness of about 10 to 500 nanometers orabout 90 to 200 nanometers. The optical layer can have at least twolayers, where adjacent layers have different thicknesses and optionallythe same or different refractive indices.

The optical element can comprise a multilayer filter. The multilayerfilter destructively interferes with light that impinges upon thearticle, where the destructive interference of the light and optionallyinteraction with one or more other layers or structures of the opticalelement (e.g., a multilayer reflector, a textured structure) impart thestructural color. In this regard, the layers of the multilayer filtercan be designed (e.g., material selection, thickness, number of layer,and the like) so that a single wavelength of light, or a particularrange of wavelengths of light, make up the structural color. Forexample, the range of wavelengths of light can be limited to a rangewithin plus or minus 30 percent or a single wavelength, or within plusor minus 20 percent of a single wavelength, or within plus or minus 10percent of a single wavelength, or within plus or minus 5 percent or asingle wavelength. The range of wavelengths can be broader to produce amore iridescent structural color.

The optical layer(s) can include multiple layers where each layerindependently comprises a material selected from: the transition metals,the metalloids, the lanthanides, and the actinides, as well as nitrides,oxynitrides, sulfides, sulfates, selenides, and tellurides of these. Thematerial can be selected to provide an index of refraction that whenoptionally combined with the other layers of the optical elementachieves the desired result. One or more layers of the optical layer canbe made of liquid crystals. Each layer of the optical layer can be madeof liquid crystals. One or more layers of the optical layer can be madeof a material such as: silicon dioxide, titanium dioxide, zinc sulfide,magnesium fluoride, tantalum pentoxide, aluminum oxide, or a combinationthereof. Each layer of the optical layer can be made of a material suchas: silicon dioxide, titanium dioxide, zinc sulfide, magnesium fluoride,tantalum pentoxide, aluminum oxide, or a combination thereof.

The optical element can be uncolored (e.g., no pigments or dyes added tothe structure or its layers), colored (e.g., pigments and/or dyes areadded to the structure or its layers (e.g., dark or black color)),reflective, and/or transparent (e.g., percent transmittance of 75percent or more). The surface of the component upon which the opticalelement is disposed can be uncolored (e.g., no pigments or dyes added tothe material), colored (e.g., pigments and/or dyes are added to thematerial (e.g., dark or black color)), reflective, and/or transparent(e.g., percent transmittance of 75 percent or more).

The optical layer(s) can be formed in a layer-by-layer manner, whereeach layer has a different index of refraction. Each layer of theoptical layer can be formed using known techniques such as physicalvapor deposition including: chemical vapor deposition, pulsed laserdeposition, evaporative deposition, sputtering deposition (e.g., radiofrequency, direct current, reactive, non-reactive), plasma enhancedchemical vapor deposition, electron beam deposition, atomic layerdeposition, molecular beam epitaxy, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir blodgett and thelike.

As mentioned above, the optical element can include one or more layersin addition to the optical layer(s). The optical element has a firstside (e.g, the side having a surface) and a second side (e.g., the sidehaving a surface), where the first side or the second side is adjacentthe surface of the component. The one or more other layers of theoptical element can be on the first side and/or the second side of theoptical element. For example, the optical element can include aprotective layer and/or a polymeric layer such as a thermoplasticpolymeric layer, where the protective layer and/or the polymeric layercan be on one or both of the first side and the second side of theoptical element. In another example, the optical element can include aprimer layer as described herein. One or more of the optional otherlayers can include a textured surface. Alternatively or in addition, oneor more optical layers of the optical element can include a texturedsurface.

A protective layer can be disposed on the first and/or second side ofthe optical layer to protect the optical layer. The protective layer ismore durable or more abrasion resistant than the optical layer. Theprotective layer is optically transparent to visible light. Theprotective layer can be on the first side of the optical element toprotect the optical layer. All or a portion of the protective layer caninclude a dye or pigment in order to alter an appearance of thestructural color. The protective layer can include silicon dioxide,glass, combinations of metal oxides, or mixtures of polymers. Theprotective layer can have a thickness of about 3 nanometers to 1millimeter.

The protective layer can be formed using physical vapor deposition,chemical vapor deposition, pulsed laser deposition, evaporativedeposition, sputtering deposition (e.g., radio frequency, directcurrent, reactive, non-reactive), plasma enhanced chemical vapordeposition, electron beam deposition, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir blodgett, andthe like. Alternatively or in addition, the protective layer can beapplied by spray coating, dip coating, brushing, spin coating, doctorblade coating, and the like.

A polymeric layer can be disposed on the first and/or the second side ofthe optical element. The polymeric layer can be used to dispose theoptical element onto an article, such as, for example, when the articledoes not include a thermoplastic material to adhere the optical element.The polymeric layer can comprise a polymeric adhesive material, such asa hot melt adhesive. The polymeric layer can be a thermoplastic materialand can include one or more layers. The thermoplastic material can beany one of the thermoplastic material described herein. The polymericlayer can be applied using various methodologies, such as spin coating,dip coating, doctor blade coating, and so on. The polymeric layer canhave a thickness of about 3 nanometer to 1 millimeter.

As described above, one or more embodiments of the present disclosureprovide articles that incorporate the optical element (e.g., single ormultilayer structures) on a side of a component of the article to impartstructural color. The optical element can be disposed onto thethermoplastic material of the side of the article, and the side of thearticle can include a textile, including a textile comprising thethermoplastic material

Having described the optical element, color, and primer layer,additional details will now be described for the optional texturedsurface. As described herein, the component includes the optical elementand the optical element can include at least one optical layer andoptionally a textured surface. The textured surface can be a surface ofa textured structure or a textured layer. The textured surface may beprovided as part of the optical element. For example, the opticalelement may comprise a textured layer or a textured structure thatcomprises the textured surface. The textured surface may be formed onthe first or second side of the optical element. The primer layer can beformed on the textured surface. For example, a side of the optical layermay be formed or modified to provide a textured surface, or a texturedlayer or textured structure can be affixed to the first or second sideof the optical element, where the primer layer can be positionedinbetween the optical element and the textured surface or on the side ofthe textured surface opposite the optical element. The textured surfacemay be provided as part of the component to which the optical element isdisposed. For example, the optical element may be disposed onto thesurface of the component where the surface of the component is atextured surface, or the surface of the component includes a texturedstructure or a textured layer affixed to it, where in either instance,the primer layer can be disposed onto the textured layer prior to theoptical element being disposed onto the component.

The textured surface (or a textured structure or textured layerincluding the textured surface) may be provided as a feature on or partof another medium, such as a transfer medium, and imparted to a side orlayer of the optical element or to the surface of the component. Forexample, a mirror image or relief form of the textured surface may beprovided on the side of a transfer medium, and the transfer mediumcontacts a side of the optical element or the surface of the componentin a way that imparts the textured surface to the optical element orarticle. While the various embodiments herein may be described withrespect to a textured surface of the optical element, it will beunderstood that the features of the textured surface, or a texturedstructure or textured layer, may be imparted in any of these ways.

The textured surface can contribute to the structural color resultingfrom the optical element. As described herein, structural coloration isimparted, at least in part, due to optical effects caused by physicalphenomena such as scattering, diffraction, reflection, interference orunequal refraction of light rays from an optical element. The texturedsurface (or its mirror image or relief) can include a plurality ofprofile features and flat or planar areas. The plurality of profilefeatures included in the textured surface, including their size, shape,orientation, spatial arrangement, etc., can affect the light scattering,diffraction, reflection, interference and/or refraction resulting fromthe optical element. The flat or planar areas included in the texturedsurface, including their size, shape, orientation, spatial arrangement,etc., can affect the light scattering, diffraction, reflection,interference and/or refraction resulting from the optical element. Thedesired structural color can be designed, at least in part, by adjustingone or more of properties of the profile features and/or flat or planarareas of the textured surface.

The profile features can extend from a side of the flat areas, so as toprovide the appearance of projections and/or depressions therein. A flatarea can be a flat planar area. A profile feature may include variouscombinations of projections and depressions. For example, a profilefeature may include a projection with one or more depressions therein, adepression with one or more projections therein, a projection with oneor more further projections thereon, a depression with one or morefurther depressions therein, and the like. The flat areas do not have tobe completely flat and can include texture, roughness, and the like. Thetexture of the flat areas may not contribute much, if any, to theimparted structural color. The texture of the flat areas typicallycontributes to the imparted structural color. For clarity, the profilefeatures and flat areas are described in reference to the profilefeatures extending above the flat areas, but the inverse (e.g.,dimensions, shapes, and the like) can apply when the profile featuresare depressions in the textured surface.

The textured surface can comprise a thermoplastic material. The profilefeatures and the flat areas can be formed using a thermoplasticmaterial. For example, when the thermoplastic material is heated aboveits softening temperature a textured surface can be formed in thethermoplastic material such as by molding, stamping, printing,compressing, cutting, etching, vacuum forming, etc., the thermoplasticmaterial to form profile features and flat areas therein. The texturedsurface can be imparted on a side of a thermoplastic material. Thetextured surface can be formed in a layer of thermoplastic material. Theprofile features and the flat areas can be made of the samethermoplastic material or a different thermoplastic material.

The textured surface generally has a length dimension extending along anx-axis, and a width dimension extending along a z-axis, and a thicknessdimension extending along a y-axis. The textured surface has a generallyplanar portion extending in a first plane that extends along the x-axisand the z-axis. A profile feature can extend outward from the firstplane, so as to extend above or below the plane x. A profile feature mayextend generally orthogonal to the first plane, or at an angle greaterto or less than 90 degrees to the first plane.

The dimension (e.g., length, width, height, diameter, depending upon theshape of the profile feature) of each profile feature can be within thenanometer to micrometer range. A textured surface can have a profilefeature and/or flat area with a dimension of about 10 nanometers toabout 500 micrometers. The profile feature can have dimensions in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. All of the dimensions of the profile feature (e.g., length,width, height, diameter, depending on the geometry) can be in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. The textured surface can have a plurality of profilefeatures having dimensions that are 1 micrometer or less. In thiscontext, the phrase “plurality of the profile features” is meant to meanthat about 50 percent or more, about 60 percent or more, about 70percent or more, about 80 percent or more, about 90 percent or more, orabout 99 percent or more of the profile features have a dimension inthis range. The profile features can have a ratio of width:height and/orlength:height dimensions of about 1:2 and 1:100, or 1:5 and 1:50, or 1:5and 1:10.

The textured surface can have a profile feature and/or flat area with adimension within the micrometer range of dimensions. A textured surfacecan have a profile feature and/or flat area with a dimension of about 1micrometer to about 500 micrometers. All of the dimensions of theprofile feature (e.g., length, width, height, diameter, depending on thegeometry) can be in the micrometer range, e.g., from about 1 micrometerto about 500 micrometers. The textured surface can have a plurality ofprofile features having dimensions that are from about 1 micrometer toabout 500 micrometer. In this context, the phrase “plurality of theprofile features” is meant to mean that about 50 percent or more, about60 percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have a dimension in this range. The height of the profilefeatures (or depth if depressions) can be about 0.1 and 50 micrometers,about 1 to 5 micrometers, or 2 to 3 micrometers. The profile featurescan have a ratio of width:height and/or length:height dimensions ofabout 1:2 and 1:100, or 1:5 and 1:50, or 1:5 and 1:10.

A textured surface can have a plurality of profile features having amixture of size dimensions within the nanometer to micrometer range(e.g., a portion of the profile features are on the nanometer scale anda portion of the profile features are on the micrometer scale). Atextured surface can have a plurality of profile features having amixture of dimensional ratios. The textured surface can have a profilefeature having one or more nanometer-scale projections or depressions ona micrometer-scale projection or depression.

The profile feature can have height and width dimensions that are withina factor of three of each other (0.33 w≤h≤3 w where w is the width and his the height of the profile feature) and/or height and lengthdimensions that are within a factor of three of each other (0.33 l≤h≤3 lwhere l is the length and h is the height of the profile feature). Theprofile feature can have a ratio of length:width that is from about 1:3to about 3:1, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1,or about 1:1.2 to about 1.2:1, or about 1:1. The width and length of theprofile features can be substantially the same or different.

The profile features can have a certain spatial arrangement. The spatialarrangement of the profile features may be uniform, such as spacedevenly apart or forming a pattern. The spatial arrangement can berandom. Adjacent profile features can be about 1 to 100 micrometersapart or about 5 to 100 micrometers apart. The desired spacing candepend, at least in part, on the size and/or shape of the profilestructures and the desired structural color effect.

The profile features can have a certain cross-sectional shape (withrespect to a plane parallel the first plane). The textured surface canhave a plurality of profile features having the same or similarcross-sectional shape. The textured surface has a plurality of profilefeatures having a mixture of different cross-sectional shapes. Thecross-sectional shapes of the profile features can include polygonal(e.g., square or triangle or rectangle cross section), circular,semi-circular, tubular, oval, random, high and low aspect ratios,overlapping profile features, and the like.

The profile feature (e.g., about 10 nanometers to 500 micrometers) caninclude an upper, convexly curved surface. The curved surface may extendsymmetrically either side of an uppermost point.

The profile feature can include protrusions from the textured surface.The profile feature can include indents (hollow areas) formed in thetextured surface. The profile feature can have a smooth, curved shape(e.g., a polygonal cross-section with curved corners).

The profile features (whether protrusions or depressions) can beapproximately conical or frusto-conical (i.e. the projections or indentsmay have horizontally or diagonally flattened tops) or have anapproximately part-spherical surface (e.g., a convex or concave surfacerespectively having a substantially even radius of curvature).

The profile features may have one or more sides or edges that extend ina direction that forms an angle to the first plane of the texturedsurface. The angle between the first plane and a side or edge of theprofile feature is about 45 degrees or less, about 30 degrees or less,about 25 degrees or less, or about 20 degrees or less. The one or moresides or edges may extend in a linear or planar orientation, or may becurved so that the angle changes as a function of distance from thefirst plane. The profile features may have one or more sides thatinclude step(s) and/or flat side(s). The profile feature can have one ormore sides (or portions thereof) that can be orthogonal or perpendicularto the first plane of the textured surface, or extend at an angle ofabout 10 degrees to 89 degrees to the first plane (90 degrees beingperpendicular or orthogonal to the first plane)). The profile featurecan have a side with a stepped configuration, where portions of the sidecan be parallel to the first plane of the textured surface or have anangle of about 1 degrees to 179 degrees (0 degrees being parallel to thefirst plane)).

The textured surface can have profile features with varying shapes(e.g., the profile features can vary in shape, height, width and lengthamong the profile features) or profile features with substantiallyuniform shapes and/or dimensions. The structural color produced by thetextured surface can be determined, at least in part, by the shape,dimensions, spacing, and the like, of the profile features.

The profile features can be shaped so as to result in a portion of thesurface (e.g., about 25 to 50 percent or more) being about normal to theincoming light when the light is incident at the normal to the firstplane of the textured surface. The profile features can be shaped so asto result in a portion of the surface (e.g., about 25 to 50 percent ormore) being about normal to the incoming light when the light isincident at an angle of up to 45 degrees to the first plane of thetextured surface.

The spatial orientation of the profile features on the textured surfaceis set to reduce distortion effects, e.g., caused by the interference ofone profile feature with another in regard to the structural color ofthe article. Since the shape, dimension, relative orientation of theprofile features can vary considerably across the textured surface, thedesired spacing and/or relative positioning for a particular area (e.g.,in the micrometer range or about 1 to 10 square micrometers) havingprofile features can be appropriately determined. As discussed herein,the shape, dimension, relative orientation of the profile featuresaffect the contours of the optical layer, so the dimensions (e.g.,thickness), index of refraction, number of layers in the optical layerare considered when designing the textured side of the texture layer.

The profile features are located in nearly random positions relative toone another across a specific area of the textured surface (e.g., in themicrometer range or about 1 to 10 square micrometers to centimeter rangeor about 0.5 to 5 square centimeters, and all range increments therein),where the randomness does not defeat the purpose of producing thestructural color. In other words, the randomness is consistent with thespacing, shape, dimension, and relative orientation of the profilefeatures, the dimensions (e.g., thickness), index of refraction, andnumber of layers in the optical layer, and the like, with the goal toachieve the structural color.

The profile features are positioned in a set manner relative to oneanother across a specific area of the textured surface to achieve thepurpose of producing the structural color. The relative positions of theprofile features do not necessarily follow a pattern, but can follow apattern consistent with the desired structural color. As mentioned aboveand herein, various parameters related to the profile features, flatareas, and optical layer can be used to position the profile features ina set manner relative to one another.

The textured surface can include micro and/or nanoscale profile featuresthat can form gratings (e.g., a diffractive grating), photonic crystalstructure, a selective mirror structure, crystal fiber structures,deformed matrix structures, spiraled coiled structures, surface gratingstructures, and combinations thereof. The textured surface can includemicro and/or nanoscale profile features that form a grating having aperiodic or non-periodic design structure to impart the structuralcolor. The micro and/or nanoscale profile features can have apeak-valley pattern of profile features and/or flat areas to produce thedesired structural color. The grading can be an Echelette grating.

The profile features and the flat areas of the textured surface in theoptical element can appear as topographical undulations in each layer ofthe optical layer. For example, referring to FIGS. 2A and 2B, an opticalelement 200 includes a textured structure 220 having a plurality ofprofile features 222 and flat areas 224. As described herein, one ormore of the profile features 222 can be projections from a surface ofthe textured structure 220 (as shown in FIG. 2A), and/or one or more ofthe profile features 222 can be depressions in a surface of the texturedstructure 220 (as shown in FIG. 2B). One or more optical layers 240 aredisposed on the side or surface of the textured structure 220 having theprofile features 222 and flat areas 224. In some embodiments, theresulting topography of the one or more optical layers 240 is notidentical to the topography of the textured structure 220, but rather,the one or more optical layers 240 can have elevated or depressedregions 242 which are either elevated or depressed relative to theheight of the planar regions 244 and which roughly correspond to thelocation of the profile features 222 of the textured structure 220. Theone or more optical layers 240 also have planar regions 244 that roughlycorrespond to the location of the flat areas 224 of the texturedstructure 220. Due to the presence of the elevated or depressed regions242 and the planar regions 244, the resultant overall topography of theoptical layer 240 can be that of an undulating or wave-like structure.The dimension, shape, and spacing of the profile features along with thenumber of layers of the optical layer, the thickness of each of thelayers, refractive index of each layer, and the type of material, can beused to produce an optical element which results in a particularstructural color. Although not shown, the primer layer can be disposedon the textured surface prior to forming the optical element.

Additional details are provided regarding the polymeric materialsreferenced herein for example, the polymers described in reference tothe article, components of the article, structures, layers, films,bladders, foams, primer layer, coating, and like the. The polymer can bea thermoset polymer or a thermoplastic polymer. The polymer can be anelastomeric polymer, including an elastomeric thermoset polymer or anelastomeric thermoplastic polymer. The polymer can be selected from:polyurethanes (including elastomeric polyurethanes, thermoplasticpolyurethanes (TPUs), and elastomeric TPUs), polyesters, polyethers,polyamides, vinyl polymers (e.g., copolymers of vinyl alcohol, vinylesters, ethylene, acrylates, methacrylates, styrene, and so on),polyacrylonitriles, polyphenylene ethers, polycarbonates, polyureas,polystyrenes, co-polymers thereof (including polyester-polyurethanes,polyether-polyurethanes, polycarbonate-polyurethanes, polyether blockpolyamides (PEBAs), and styrene block copolymers), and any combinationthereof, as described herein. The polymer can include one or morepolymers selected from the group consisting of polyesters, polyethers,polyamides, polyurethanes, polyolefins copolymers of each, andcombinations thereof.

The term “polymer” refers to a chemical compound formed of a pluralityof repeating structural units referred to as monomers. Polymers oftenare formed by a polymerization reaction in which the plurality ofstructural units become covalently bonded together. When the monomerunits forming the polymer all have the same chemical structure, thepolymer is a homopolymer. When the polymer includes two or more monomerunits having different chemical structures, the polymer is a copolymer.One example of a type of copolymer is a terpolymer, which includes threedifferent types of monomer units. The co-polymer can include two or moredifferent monomers randomly distributed in the polymer (e.g., a randomco-polymer). Alternatively, one or more blocks containing a plurality ofa first type of monomer can be bonded to one or more blocks containing aplurality of a second type of monomer, forming a block copolymer. Asingle monomer unit can include one or more different chemicalfunctional groups.

Polymers having repeating units which include two or more types ofchemical functional groups can be referred to as having two or moresegments. For example, a polymer having repeating units of the samechemical structure can be referred to as having repeating segments.Segments are commonly described as being relatively harder or softerbased on their chemical structures, and it is common for polymers toinclude relatively harder segments and relatively softer segments bondedto each other in a single monomeric unit or in different monomericunits. When the polymer includes repeating segments, physicalinteractions or chemical bonds can be present within the segments orbetween the segments or both within and between the segments. Examplesof segments often referred to as hard segments include segmentsincluding a urethane linkage, which can be formed from reacting anisocyanate with a polyol to form a polyurethane. Examples of segmentsoften referred to as soft segments include segments including an alkoxyfunctional group, such as segments including ether or ester functionalgroups, and polyester segments. Segments can be referred to based on thename of the functional group present in the segment (e.g., a polyethersegment, a polyester segment), as well as based on the name of thechemical structure which was reacted in order to form the segment (e.g.,a polyol-derived segment, an isocyanate-derived segment). When referringto segments of a particular functional group or of a particular chemicalstructure from which the segment was derived, it is understood that thepolymer can contain up to 10 mole percent of segments of otherfunctional groups or derived from other chemical structures. Forexample, as used herein, a polyether segment is understood to include upto 10 mole percent of non-polyether segments.

As previously described, the polymer can be a thermoplastic polymer. Ingeneral, a thermoplastic polymer softens or melts when heated andreturns to a solid state when cooled. The thermoplastic polymertransitions from a solid state to a softened state when its temperatureis increased to a temperature at or above its softening temperature, anda liquid state when its temperature is increased to a temperature at orabove its melting temperature. When sufficiently cooled, thethermoplastic polymer transitions from the softened or liquid state tothe solid state. As such, the thermoplastic polymer may be softened ormelted, molded, cooled, re-softened or re-melted, re-molded, and cooledagain through multiple cycles. For amorphous thermoplastic polymers, thesolid state is understood to be the “rubbery” state above the glasstransition temperature of the polymer. The thermoplastic polymer canhave a melting temperature from about 90 degrees C. to about 190 degreesC. when determined in accordance with ASTM D3418-97 as described hereinbelow, and includes all subranges therein in increments of 1 degree. Thethermoplastic polymer can have a melting temperature from about 93degrees C. to about 99 degrees C. when determined in accordance withASTM D3418-97 as described herein below. The thermoplastic polymer canhave a melting temperature from about 112 degrees C. to about 118degrees C. when determined in accordance with ASTM D3418-97 as describedherein below.

The glass transition temperature is the temperature at which anamorphous polymer transitions from a relatively brittle “glassy” stateto a relatively more flexible “rubbery” state. The thermoplastic polymercan have a glass transition temperature from about −20 degrees C. toabout 30 degrees C. when determined in accordance with ASTM D3418-97 asdescribed herein below. The thermoplastic polymer can have a glasstransition temperature (from about −13 degree C. to about −7 degrees C.when determined in accordance with ASTM D3418-97 as described hereinbelow. The thermoplastic polymer can have a glass transition temperaturefrom about 17 degrees C. to about 23 degrees C. when determined inaccordance with ASTM D3418-97 as described herein below.

The thermoplastic polymer can have a melt flow index from about 10 toabout 30 cubic centimeters per 10 minutes (cm3/10 min) when tested inaccordance with ASTM D1238-13 as described herein below at 160 degreesC. using a weight of 2.16 kilograms (kg). The thermoplastic polymer canhave a melt flow index from about 22 cm3/10 min to about 28 cm3/10 minwhen tested in accordance with ASTM D1238-13 as described herein belowat 160 degrees C. using a weight of 2.16 kg.

The thermoplastic polymer can have a cold Ross flex test result of about120,000 to about 180,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below. Thethermoplastic polymer can have a cold Ross flex test result of about140,000 to about 160,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below.

The thermoplastic polymer can have a modulus from about 5 megaPascals(MPa) to about 100 MPa when determined on a thermoformed plaque inaccordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubberand Thermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below. The thermoplastic polymer can havea modulus from about 20 MPa to about 80 MPa when determined on athermoformed plaque in accordance with ASTM D412-98 Standard TestMethods for Vulcanized Rubber and Thermoplastic Rubbers andThermoplastic Elastomers-Tension with modifications described hereinbelow.

The polymer can be a thermoset polymer. As used herein, a “thermosetpolymer” is understood to refer to a polymer which cannot be heated andmelted, as its melting temperature is at or above its decompositiontemperature. A “thermoset material” refers to a material which comprisesat least one thermoset polymer. The thermoset polymer and/or thermosetmaterial can be prepared from a precursor (e.g., an uncured or partiallycured polymer or material) using thermal energy and/or actinic radiation(e.g., ultraviolet radiation, visible radiation, high energy radiation,infrared radiation) to form a partially cured or fully cured polymer ormaterial which no longer remains fully thermoplastic. In some cases, thecured or partially cured polymer or material may remain thermoelasticproperties, in that it is possible to partially soften and mold thepolymer or material at elevated temperatures and/or pressures, but it isnot possible to melt the polymer or material. The curing can bepromoted, for example, with the use of high pressure and/or a catalyst.In many examples, the curing process is irreversible since it results incross-linking and/or polymerization reactions of the precursors. Theuncured or partially cured polymers or materials can be malleable orliquid prior to curing. In some cases, the uncured or partially curedpolymers or materials can be molded into their final shape, or used asadhesives. Once hardened, a thermoset polymer or material cannot bere-melted in order to be reshaped. The textured surface can be formed bypartially or fully curing an uncured precursor material to lock in thetextured surface.

Polyurethane

The polymer can be a polyurethane, such as a thermoplastic polyurethane(also referred to as “TPU”). Alternatively, the polymer can be athermoset polyurethane. Additionally, polyurethane can be an elastomericpolyurethane, including an elastomeric TPU or an elastomeric thermosetpolyurethane. The elastomeric polyurethane can include hard and softsegments. The hard segments can comprise or consist of urethane segments(e.g., isocyanate-derived segments). The soft segments can comprise orconsist of alkoxy segments (e.g., polyol-derived segments includingpolyether segments, or polyester segments, or a combination of polyethersegments and polyester segments). The polyurethane can comprise orconsist essentially of an elastomeric polyurethane having repeating hardsegments and repeating soft segments.

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce polymer chainshaving carbamate linkages (—N(CO)O—) as illustrated below in Formula 1,where the isocyanate(s) each preferably include two or more isocyanate(—NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups permolecule (although, mono-functional isocyanates can also be optionallyincluded, e.g., as chain terminating units).

Each R1 group and R2 group independently is an aliphatic or aromaticgroup. Optionally, each R2 can be a relatively hydrophilic group,including a group having one or more hydroxyl groups.

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates, increasing thelength of the hard segment. This can produce polyurethane polymer chainsas illustrated below in Formula 2, where R3 includes the chain extender.As with each R1 and R2, each R3 independently is an aliphatic oraromatic functional group.

Each R1 group in Formulas 1 and 2 can independently include a linear orbranched group having from 3 to 30 carbon atoms, based on the particularisocyanate(s) used, and can be aliphatic, aromatic, or include acombination of aliphatic portions(s) and aromatic portion(s). The term“aliphatic” refers to a saturated or unsaturated organic molecule orportion of a molecule that does not include a cyclically conjugated ringsystem having delocalized pi electrons. In comparison, the term“aromatic” refers to an organic molecule or portion of a molecule havinga cyclically conjugated ring system with delocalized pi electrons, whichexhibits greater stability than a hypothetical ring system havinglocalized pi electrons.

Each R1 group can be present in an amount of about 5 percent to about 85percent by weight, from about 5 percent to about 70 percent by weight,or from about 10 percent to about 50 percent by weight, based on thetotal weight of the reactant compounds or monomers which form thepolymer.

In aliphatic embodiments (from aliphatic isocyanate(s)), each R1 groupcan include a linear aliphatic group, a branched aliphatic group, acycloaliphatic group, or combinations thereof. For instance, each R1group can include a linear or branched alkylene group having from 3 to20 carbon atoms (e.g., an alkylene having from 4 to 15 carbon atoms, oran alkylene having from 6 to 10 carbon atoms), one or more cycloalkylenegroups having from 3 to 8 carbon atoms (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinationsthereof. The term “alkene” or “alkylene” as used herein refers to abivalent hydrocarbon. When used in association with the term Cn it meansthe alkene or alkylene group has “n” carbon atoms. For example, C1-6alkylene refers to an alkylene group having, e.g., 1, 2, 3, 4, 5, or 6carbon atoms.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane polymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

The isocyanate-derived segments can include segments derived fromaliphatic diisocyanate. A majority of the isocyanate-derived segmentscan comprise segments derived from aliphatic diisocyanates. At least 90%of the isocyanate-derived segments are derived from aliphaticdiisocyanates. The isocyanate-derived segments can consist essentiallyof segments derived from aliphatic diisocyanates. The aliphaticdiisocyanate-derived segments can be derived substantially (e.g., about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more) from linearaliphatic diisocyanates. At least 80% of the aliphaticdiisocyanate-derived segments can be derived from aliphaticdiisocyanates that are free of side chains. The segments derived fromaliphatic diisocyanates can include linear aliphatic diisocyanateshaving from 2 to 10 carbon atoms.

When the isocyanate-derived segments are derived from aromaticisocyanate(s)), each R1 group can include one or more aromatic groups,such as phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unlessotherwise indicated, an aromatic group can be an unsubstituted aromaticgroup or a substituted aromatic group, and can also includeheteroaromatic groups. “Heteroaromatic” refers to monocyclic orpolycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ringsystems, where one to four ring atoms are selected from oxygen,nitrogen, or sulfur, and the remaining ring atoms are carbon, and wherethe ring system is joined to the remainder of the molecule by any of thering atoms. Examples of suitable heteroaryl groups include pyridyl,pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl,tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl,quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, andbenzothiazolyl groups.

Examples of suitable aromatic diisocyanates for producing thepolyurethane polymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI),3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyldiisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate, andcombinations thereof. The polymer chains can be substantially free ofaromatic groups.

The polyurethane polymer chains can be produced from diisocyanatesincluding HMDI, TDI, MDI, H12 aliphatics, and combinations thereof. Forexample, the polyurethane can comprise one or more polyurethane polymerchains produced from diisocyanates including HMDI, TDI, MDI, H12aliphatics, and combinations thereof.

Polyurethane chains which are at least partially crosslinked or whichcan be crosslinked, can be used in accordance with the presentdisclosure. It is possible to produce crosslinked or crosslinkablepolyurethane chains by reacting multi-functional isocyanates to form thepolyurethane. Examples of suitable triisocyanates for producing thepolyurethane chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

The R3 group in Formula 2 can include a linear or branched group havingfrom 2 to 10 carbon atoms, based on the particular chain extender polyolused, and can be, for example, aliphatic, aromatic, or an ether orpolyether. Examples of suitable chain extender polyols for producing thepolyurethane include ethylene glycol, lower oligomers of ethylene glycol(e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol),1,2-propylene glycol, 1,3-propylene glycol, lower oligomers of propyleneglycol (e.g., dipropylene glycol, tripropylene glycol, andtetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol,1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol,1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylatedaromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone andresorcinol, xylene-a,a-diols, bis(2-hydroxyethyl) ethers ofxylene-a,a-diols, and combinations thereof.

The R2 group in Formula 1 and 2 can include a polyether group, apolyester group, a polycarbonate group, an aliphatic group, or anaromatic group. Each R2 group can be present in an amount of about 5percent to about 85 percent by weight, from about 5 percent to about 70percent by weight, or from about 10 percent to about 50 percent byweight, based on the total weight of the reactant monomers.

At least one R2 group of the polyurethane includes a polyether segment(i.e., a segment having one or more ether groups). Suitable polyethergroups include, but are not limited to, polyethylene oxide (PEO),polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof. The term“alkyl” as used herein refers to straight chained and branched saturatedhydrocarbon groups containing one to thirty carbon atoms, for example,one to twenty carbon atoms, or one to ten carbon atoms. When used inassociation with the term Cn it means the alkyl group has “n” carbonatoms. For example, C4 alkyl refers to an alkyl group that has 4 carbonatoms. C1-7 alkyl refers to an alkyl group having a number of carbonatoms encompassing the entire range (i.e., 1 to 7 carbon atoms), as wellas all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7carbon atoms). Non-limiting examples of alkyl groups include, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl(1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unlessotherwise indicated, an alkyl group can be an unsubstituted alkyl groupor a substituted alkyl group.

In some examples of the polyurethane, the at least one R2 group includesa polyester group. The polyester group can be derived from thepolyesterification of one or more dihydric alcohols (e.g., ethyleneglycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol,1,3-butanediol, 2-methylpentanediol 1,5-diethylene glycol,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with one or moredicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid,suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaicacid, thiodipropionic acid and citraconic acid and combinationsthereof). The polyester group also can be derived from polycarbonateprepolymers, such as poly(hexamethylene carbonate) glycol,poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol,and poly(nonanemethylene carbonate) glycol. Suitable polyesters caninclude, for example, polyethylene adipate (PEA), poly(1,4-butyleneadipate), poly(tetramethylene adipate), poly(hexamethylene adipate),polycaprolactone, polyhexamethylene carbonate, poly(propylenecarbonate), poly(tetramethylene carbonate), poly(nonanemethylenecarbonate), and combinations thereof.

At least one R2 group can include a polycarbonate group. Thepolycarbonate group can be derived from the reaction of one or moredihydric alcohols (e.g., ethylene glycol, 1,3-propylene glycol,1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol,2-methylpentanediol 1,5-diethylene glycol, 1,5-pentanediol,1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, andcombinations thereof) with ethylene carbonate.

The aliphatic group can be linear and can include, for example, analkylene chain having from 1 to 20 carbon atoms or an alkenylene chainhaving from 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, ethenylene, propenylene,butenylene, pentenylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). Theterm “alkene” or “alkylene” refers to a bivalent hydrocarbon. The term“alkenylene” refers to a bivalent hydrocarbon molecule or portion of amolecule having at least one double bond.

The aliphatic and aromatic groups can be substituted with one or morependant relatively hydrophilic and/or charged groups. The pendanthydrophilic group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9,10 or more) hydroxyl groups. The pendant hydrophilic group includes oneor more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, thealiphatic group can include one or more polyacrylic acid group. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, thependant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7,8, 9, 10 or more) phosphate groups. In some examples, the pendanthydrophilic group includes one or more ammonium groups (e.g., tertiaryand/or quaternary ammonium). In other examples, the pendant hydrophilicgroup includes one or more zwitterionic groups (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonate groups such as aphosphatidylcholine group).

The R2 group can include charged groups that are capable of binding to acounterion to ionically crosslink the polymer and form ionomers. Forexample, R2 is an aliphatic or aromatic group having pendant amino,carbon/late, sulfonate, phosphate, ammonium, or zwitterionic groups, orcombinations thereof.

When a pendant hydrophilic group is present, the pendant hydrophilicgroup can be at least one polyether group, such as two polyether groups.In other cases, the pendant hydrophilic group is at least one polyester.The pendant hydrophilic group can be a polylactone group (e.g.,polyvinylpyrrolidone). Each carbon atom of the pendant hydrophilic groupcan optionally be substituted with, e.g., an alkyl group having from 1to 6 carbon atoms. The aliphatic and aromatic groups can be graftpolymeric groups, wherein the pendant groups are homopolymeric groups(e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

The pendant hydrophilic group can be a polyether group (e.g., apolyethylene oxide (PEO) group, a polyethylene glycol (PEG) group), apolyvinylpyrrolidone group, a polyacrylic acid group, or combinationsthereof.

The pendant hydrophilic group can be bonded to the aliphatic group oraromatic group through a linker. The linker can be any bifunctionalsmall molecule (e.g., one having from 1 to 20 carbon atoms) capable oflinking the pendant hydrophilic group to the aliphatic or aromaticgroup. For example, the linker can include a diisocyanate group, aspreviously described herein, which when linked to the pendanthydrophilic group and to the aliphatic or aromatic group forms acarbamate bond. The linker can be 4,4′-diphenylmethane diisocyanate(MDI), as shown below.

The pendant hydrophilic group can be a polyethylene oxide group and thelinking group can be MDI, as shown below.

The pendant hydrophilic group can be functionalized to enable it to bondto the aliphatic or aromatic group, optionally through the linker. Forexample, when the pendant hydrophilic group includes an alkene group,which can undergo a Michael addition with a sulfhydryl-containingbifunctional molecule (i.e., a molecule having a second reactive group,such as a hydroxyl group or amino group), resulting in a hydrophilicgroup that can react with the polymer backbone, optionally through thelinker, using the second reactive group. For example, when the pendanthydrophilic group is a polyvinylpyrrolidone group, it can react with thesulfhydryl group on mercaptoethanol to result in hydroxyl-functionalizedpolyvinylpyrrolidone, as shown below.

At least one R2 group in the polyurethane can include apolytetramethylene oxide group. At least one R2 group of thepolyurethane can include an aliphatic polyol group functionalized with apolyethylene oxide group or polyvinylpyrrolidone group, such as thepolyols described in E.P. Patent No. 2 462 908, which is herebyincorporated by reference. For example, the R2 group can be derived fromthe reaction product of a polyol (e.g., pentaerythritol or2,2,3-trihydroxypropanol) and either MDI-derivatized methoxypolyethyleneglycol (to obtain compounds as shown in Formulas 6 or 7) or withMDI-derivatized polyvinylpyrrolidone (to obtain compounds as shown inFormulas 8 or 9) that had been previously been reacted withmercaptoethanol, as shown below.

At least one R2 of the polyurethane can be a polysiloxane, In thesecases, the R2 group can be derived from a silicone monomer of Formula10, such as a silicone monomer disclosed in U.S. Pat. No. 5,969,076,which is hereby incorporated by reference:

wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or10); each R4 independently is hydrogen, an alkyl group having from 1 to18 carbon atoms, an alkenyl group having from 2 to 18 carbon atoms,aryl, or polyether; and each R5 independently is an alkylene grouphaving from 1 to 10 carbon atoms, polyether, or polyurethane.

Each R4 group can independently be a H, an alkyl group having from 1 to10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, anaryl group having from 1 to 6 carbon atoms, polyethylene, polypropylene,or polybutylene group. Each R4 group can independently be selected fromthe group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, s-butyl, t-butyl, ethenyl, propenyl, phenyl, and polyethylenegroups.

Each R5 group can independently include an alkylene group having from 1to 10 carbon atoms (e.g., a methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, or decylene group).Each R5 group can be a polyether group (e.g., a polyethylene,polypropylene, or polybutylene group). Each R5 group can be apolyurethane group.

Optionally, the polyurethane can include an at least partiallycrosslinked polymeric network that includes polymer chains that arederivatives of polyurethane. The level of crosslinking can be such thatthe polyurethane retains thermoplastic properties (i.e., the crosslinkedthermoplastic polyurethane can be melted and re-solidified under theprocessing conditions described herein). The crosslinked polyurethanecan be a thermoset polymer. This crosslinked polymeric network can beproduced by polymerizing one or more isocyanates with one or morepolyamino compounds, polysulfhydryl compounds, or combinations thereof,as shown in Formulas 11 and 12, below:

wherein the variables are as described above. Additionally, theisocyanates can also be chain extended with one or more polyamino orpolythiol chain extenders to bridge two or more isocyanates, such aspreviously described for the polyurethanes of Formula 2.

The polyurethane chain can be physically crosslinked to anotherpolyurethane chain through e.g., nonpolar or polar interactions betweenthe urethane or carbamate groups of the polymers (the hard segments).The R1 group in Formula 1, and the R1 and R3 groups in Formula 2, formthe portion of the polymer often referred to as the “hard segment”, andthe R2 group forms the portion of the polymer often referred to as the“soft segment”. The soft segment is covalently bonded to the hardsegment. The polyurethane having physically crosslinked hard and softsegments can be a hydrophilic polyurethane (i.e., a polyurethane,including a thermoplastic polyurethane, including hydrophilic groups asdisclosed herein).

The polyurethane can be a thermoplastic polyurethane composed of MDI,PTMO, and 1,4-butylene glycol, as described in U.S. Pat. No. 4,523,005.Commercially available polyurethanes suitable for the present useinclude, but are not limited to those under the tradename “SANCURE”(e.g., the “SANCURE” series of polymer such as “SANCURE” 20025F) or“TECOPHILIC” (e.g., TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60)(Lubrizol, Countryside, Ill., USA), “PELLETHANE” 2355-85ATP and2355-95AE (Dow Chemical Company of Midland, Mich., USA.), “ESTANE”(e.g., ALR G 500, or 58213; Lubrizol, Countryside, Ill., USA).

One or more of the polyurethanes (e.g., those used in the primer as thecoating (e.g., water-dispersible polyurethane)) can be produced bypolymerizing one or more isocyanates with one or more polyols to producecopolymer chains having carbamate linkages (—N(C═O)O—) and one or morewater-dispersible enhancing moieties, where the polymer chain includesone or more water-dispersible enhancing moieties (e.g., a monomer inpolymer chain). The water-dispersible polyurethane can also be referredto as “a water-borne polyurethane polymer dispersion.” Thewater-dispersible enhancing moiety can be added to the chain of Formula1 or 2 (e.g., within the chain and/or onto the chain as a side chain).Inclusion of the water-dispersible enhancing moiety enables theformation of a water-borne polyurethane dispersion. The term“water-borne” herein means the continuous phase of the dispersion orformulation of about 50 weight percent to 100 weight percent water,about 60 weight percent to 100 weight percent water, about 70 weightpercent to 100 weight percent water, or about 100 weight percent water.The term “water-borne dispersion” refers to a dispersion of a component(e.g., polymer, cross-linker, and the like) in water withoutco-solvents. The co-solvent can be used in the water-borne dispersionand the co-solvent can be an organic solvent. Additional detailregarding the polymers, polyurethanes, isocyantes and the polyols areprovided below.

The polyurethane (e.g., a water-borne polyurethane polymer dispersion)can include one or more water-dispersible enhancing moieties. Thewater-dispersible enhancing moiety can have at least one hydrophilic(e.g., poly(ethylene oxide)), ionic or potentially ionic group to assistdispersion of the polyurethane, thereby enhancing the stability of thedispersions. A water-dispersible polyurethane can be formed byincorporating a moiety bearing at least one hydrophilic group or a groupthat can be made hydrophilic (e.g., by chemical modifications such asneutralization) into the polymer chain. For example, these compounds canbe nonionic, anionic, cationic or zwitterionic or the combinationthereof. In one example, anionic groups such as carboxylic acid groupscan be incorporated into the chain in an inactive form and subsequentlyactivated by a salt-forming compound, such as a tertiary amine. Otherwater-dispersible enhancing moieties can also be reacted into thebackbone through urethane linkages or urea linkages, including lateralor terminal hydrophilic ethylene oxide or ureido units.

The water-dispersible enhancing moiety can be a one that includescarboxyl groups. Water-dispersible enhancing moiety that include acarboxyl group can be formed from hydroxy-carboxylic acids having thegeneral formula (HO)xQ(COOH)y, where Q can be a straight or branchedbivalent hydrocarbon radical containing 1 to 12 carbon atoms, and x andy can each independently be 1 to 3. Illustrative examples includedimethylolpropanoic acid (DMPA), dimethylol butanoic acid (DMBA), citricacid, tartaric acid, glycolic acid, lactic acid, malic acid,dihydroxymalic acid, dihydroxytartaric acid, and the like, and mixturesthereof.

The water-dispersible enhancing moiety can include reactive polymericpolyol components that contain pendant anionic groups that can bepolymerized into the backbone to impart water dispersiblecharacteristics to the polyurethane. Anionic functional polymericpolyols can include anionic polyester polyols, anionic polyetherpolyols, and anionic polycarbonate polyols, where additional detail isprovided in U.S. Pat. No. 5,334,690.

The water-dispersible enhancing moiety can include a side chainhydrophilic monomer. For example, the water-dispersible enhancing moietyincluding the side chain hydrophilic monomer can include alkylene oxidepolymers and copolymers in which the alkylene oxide groups have from2-10 carbon atoms as shown in U.S. Pat. No. 6,897,281. Additional typesof water-dispersible enhancing moieties can include thioglycolic acid,2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol,and the like, and mixtures thereof. Additional details regardingwater-dispersible enhancing moieties can be found in U.S. Pat. No.7,476,705.

Polyamides

The polymer can comprise a polyamide, such as a thermoplastic polyamide,or a thermoset polyamide. The polyamide can be an elastomeric polyamide,including an elastomeric thermoplastic polyamide or an elastomericthermoset polyamide. The polyamide can be a polyamide homopolymer havingrepeating polyamide segments of the same chemical structure.Alternatively, the polyamide can comprise a number of polyamide segmentshaving different polyamide chemical structures (e.g., polyamide 6segments, polyamide 11 segments, polyamide 12 segments, polyamide 66segments, etc.). The polyamide segments having different chemicalstructure can be arranged randomly, or can be arranged as repeatingblocks.

The polyamide can be a co-polyamide (i.e., a co-polymer includingpolyamide segments and non-polyamide segments). The polyamide segmentsof the co-polyamide can comprise or consist of polyamide 6 segments,polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, orany combination thereof. The polyamide segments of the co-polyamide canbe arranged randomly, or can be arranged as repeating segments. Thepolyamide segments can comprise or consist of polyamide 6 segments, orpolyamide 12 segments, or both polyamide 6 segment and polyamide 12segments. In the example where the polyamide segments of theco-polyamide include of polyamide 6 segments and polyamide 12 segments,the segments can be arranged randomly. The non-polyamide segments of theco-polyamide can comprise or consist of polyether segments, polyestersegments, or both polyether segments and polyester segments. Theco-polyamide can be a block co-polyamide, or can be a randomco-polyamide. The copolyamide can be formed from the polycondensation ofa polyamide oligomer or prepolymer with a second oligomer prepolymer toform a copolyamide (i.e., a co-polymer including polyamide segments.Optionally, the second prepolymer can be a hydrophilic prepolymer.

The polyamide can be a polyamide-containing block co-polymer. Forexample, the block co-polymer can have repeating hard segments, andrepeating soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thepolyamide-containing block co-polymer can be an elastomeric co-polyamidecomprising or consisting of polyamide-containing block co-polymershaving repeating hard segments and repeating soft segments. In blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within thesegments or between the segments or both within and between thesegments.

The polyamide itself, or the polyamide segment of thepolyamide-containing block co-polymer can be derived from thecondensation of polyamide prepolymers, such as lactams, amino acids,and/or diamino compounds with dicarboxylic acids, or activated formsthereof. The resulting polyamide segments include amide linkages(—(CO)NH—). The term “amino acid” refers to a molecule having at leastone amino group and at least one carboxyl group. Each polyamide segmentof the polyamide can be the same or different.

The polyamide or the polyamide segment of the polyamide-containing blockco-polymer can be derived from the polycondensation of lactams and/oramino acids, and can include an amide segment having a structure shownin Formula 13, below, wherein R6 group represents the portion of thepolyamide derived from the lactam or amino acid.

The R6 group can be derived from a lactam. The R6 group can be derivedfrom a lactam group having from 3 to 20 carbon atoms, or a lactam grouphaving from 4 to 15 carbon atoms, or a lactam group having from 6 to 12carbon atoms. The R6 group can be derived from caprolactam orlaurolactam. The R6 group can be derived from one or more amino acids.The R6 group can be derived from an amino acid group having from 4 to 25carbon atoms, or an amino acid group having from 5 to 20 carbon atoms,or an amino acid group having from 8 to 15 carbon atoms. The R6 groupcan be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

Optionally, in order to increase the relative degree of hydrophilicityof the polyamide-containing block co-polymer, Formula 13 can include apolyamide-polyether block copolymer segment, as shown below:

wherein m is 3-20, and n is 1-8. Optionally, m is 4-15, or 6-12 (e.g.,6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. For example, m can be11 or 12, and n can be 1 or 3. The polyamide or the polyamide segment ofthe polyamide-containing block co-polymer can be derived from thecondensation of diamino compounds with dicarboxylic acids, or activatedforms thereof, and can include an amide segment having a structure shownin Formula 15, below, wherein the R7 group represents the portion of thepolyamide derived from the diamino compound, and the R8 group representsthe portion derived from the dicarboxylic acid compound:

The R7 group can be derived from a diamino compound that includes analiphatic group having from 4 to 15 carbon atoms, or from 5 to 10 carbonatoms, or from 6 to 9 carbon atoms. The diamino compound can include anaromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Suitablediamino compounds from which the R7 group can be derived include, butare not limited to, hexamethylene diamine (HMD), tetramethylene diamine,trimethyl hexamethylene diamine (TMD), m-xylylene diamine (MXD), and1,5-pentamine diamine. The R8 group can be derived from a dicarboxylicacid or activated form thereof, including an aliphatic group having from4 to 15 carbon atoms, or from 5 to 12 carbon atoms, or from 6 to 10carbon atoms. The dicarboxylic acid or activated form thereof from whichR8 can be derived includes an aromatic group, such as phenyl, naphthyl,xylyl, and tolyl groups. Suitable carboxylic acids or activated formsthereof from which R8 can be derived include adipic acid, sebacic acid,terephthalic acid, and isophthalic acid. The polyamide chain can besubstantially free of aromatic groups.

Each polyamide segment of the polyamide (including thepolyamide-containing block co-polymer) can be independently derived froma polyamide prepolymer selected from the group consisting of12-aminolauric acid, caprolactam, hexamethylene diamine and adipic acid.

The polyamide can comprise or consist essentially of apoly(ether-block-amide). The poly(ether-block-amide) can be formed fromthe polycondensation of a carboxylic acid terminated polyamideprepolymer and a hydroxyl terminated polyether prepolymer to form apoly(ether-block-amide), as shown in Formula 16:

The poly(ether block amide) polymer can be prepared by polycondensationof polyamide blocks containing reactive ends with polyether blockscontaining reactive ends. Examples include: 1) polyamide blockscontaining diamine chain ends with polyoxyalkylene blocks containingcarboxylic chain ends; 2) polyamide blocks containing dicarboxylic chainends with polyoxyalkylene blocks containing diamine chain ends obtainedby cyanoethylation and hydrogenation of aliphatic dihydroxylatedalpha-omega polyoxyalkylenes known as polyether diols; 3) polyamideblocks containing dicarboxylic chain ends with polyether diols, theproducts obtained in this particular case being polyetheresteramides.The polyamide block of the poly(ether-block-amide) can be derived fromlactams, amino acids, and/or diamino compounds with dicarboxylic acidsas previously described. The polyether block can be derived from one ormore polyethers selected from the group consisting of polyethylene oxide(PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks comprising dicarboxylic chain ends derived from thecondensation of α, ω-aminocarboxylic acids, of lactams or ofdicarboxylic acids and diamines in the presence of a chain-limitingdicarboxylic acid. In poly(ether block amide) polymers of this type, aα, ω-aminocarboxylic acid such as aminoundecanoic acid can be used; alactam such as caprolactam or lauryllactam can be used; a dicarboxylicacid such as adipic acid, decanedioic acid or dodecanedioic acid can beused; and a diamine such as hexamethylenediamine can be used; or variouscombinations of any of the foregoing. The copolymer can comprisepolyamide blocks comprising polyamide 12 or of polyamide 6.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of one or more α,ω-aminocarboxylic acids and/or of one or more lactams containing from 6to 12 carbon atoms in the presence of a dicarboxylic acid containingfrom 4 to 12 carbon atoms, and are of low mass, i.e., they have anumber-average molecular weight of from 400 to 1000. In poly(ether blockamide) polymers of this type, an α, ω-aminocarboxylic acid such asaminoundecanoic acid or aminododecanoic acid can be used; a dicarboxylicacid such as adipic acid, sebacic acid, isophthalic acid, butanedioicacid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium orlithium salt of sulphoisophthalic acid, dimerized fatty acids (thesedimerized fatty acids have a dimer content of at least 98 weight percentand are preferably hydrogenated) and dodecanedioic acidHOOC—(CH2)10—COOH can be used; and a lactam such as caprolactam andlauryllactam can be used; or various combinations of any of theforegoing. The copolymer can comprise polyamide blocks obtained bycondensation of lauryllactam in the presence of adipic acid ordodecanedioic acid and with a number average molecular weight of atleast 750 have a melting temperature of from about 127 to about 130degrees C. The various constituents of the polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., or from about 90 degrees C. to about 135 degrees C.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of at least one α,ω-aminocarboxylic acid (or a lactam), at least one diamine and at leastone dicarboxylic acid. In copolymers of this type, a α,ω-aminocarboxylicacid, the lactam and the dicarboxylic acid can be chosen from thosedescribed herein above and the diamine such as an aliphatic diaminecontaining from 6 to 12 atoms and can be acyclic and/or saturated cyclicsuch as, but not limited to, hexamethylenediamine, piperazine,1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylenediamine,octamethylene-diamine, decamethylenediamine, dodecamethylenediamine,1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols,isophoronediamine (IPD), methylpentamethylenediamine (MPDM),bis(aminocyclohexyl)methane (BACM) andbis(3-methyl-4-aminocyclohexyl)methane (BMACM) can be used.

The polyamide can be a thermoplastic polyamide and the constituents ofthe polyamide block and their proportion can be chosen in order toobtain a melting temperature of less than 150 degrees C., such as amelting point of from about 90 degrees C. to about 135 degrees C. Thevarious constituents of the thermoplastic polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., such as from about and 90 degrees C. to about 135degrees C.

The number average molar mass of the polyamide blocks can be from about300 grams per mole to about 15,000 grams per mole, from about 500 gramsper mole to about 10,000 grams per mole, from about 500 grams per moleto about 6,000 grams per mole, from about 500 grams per mole to about5,000 grams per mole, or from about 600 grams per mole to about 5,000grams per mole. The number average molecular weight of the polyetherblock can range from about 100 to about 6,000, from about 400 to about3000, or from about 200 to about 3,000. The polyether (PE) content (x)of the poly(ether block amide) polymer can be from about 0.05 to about0.8 (i.e., from about 5 mole percent to about 80 mole percent). Thepolyether blocks can be present in the polyamide in an amount of fromabout 10 weight percent to about 50 weight percent, from about 20 weightpercent to about 40 weight percent, or from about 30 weight percent toabout 40 weight percent. The polyamide blocks can be present in thepolyamide in an amount of from about 50 weight percent to about 90weight percent, from about 60 weight percent to about 80 weight percent,or from about 70 weight percent to about 90 weight percent.

The polyether blocks can contain units other than ethylene oxide units,such as, for example, propylene oxide or polytetrahydrofuran (whichleads to polytetramethylene glycol sequences). It is also possible touse simultaneously PEG blocks, i.e., those consisting of ethylene oxideunits, polypropylene glycol (PPG) blocks, i.e. those consisting ofpropylene oxide units, and poly(tetramethylene ether)glycol (PTMG)blocks, i.e. those consisting of tetramethylene glycol units, also knownas polytetrahydrofuran. PPG or PTMG blocks are advantageously used. Theamount of polyether blocks in these copolymers containing polyamide andpolyether blocks can be from about 10 weight percent to about 50 weightpercent of the copolymer, or from about 35 weight percent to about 50weight percent.

The copolymers containing polyamide blocks and polyether blocks can beprepared by any means for attaching the polyamide blocks and thepolyether blocks. In practice, two processes are essentially used, onebeing a 2-step process and the other a one-step process.

In the two-step process, the polyamide blocks having dicarboxylic chainends are prepared first, and then, in a second step, these polyamideblocks are linked to the polyether blocks. The polyamide blocks havingdicarboxylic chain ends are derived from the condensation of polyamideprecursors in the presence of a chain-stopper dicarboxylic acid. If thepolyamide precursors are only lactams or α,ω-aminocarboxylic acids, adicarboxylic acid is added. If the precursors already comprise adicarboxylic acid, this is used in excess with respect to thestoichiometry of the diamines. The reaction usually takes place fromabout 180 to about 300 degrees C., such as from about 200 degrees toabout 290 degrees C., and the pressure in the reactor can be set fromabout 5 to about 30 bar and maintained for approximately 2 to 3 hours.The pressure in the reactor is slowly reduced to atmospheric pressureand then the excess water is distilled off, for example for one or twohours.

Once the polyamide having carboxylic acid end groups has been prepared,the polyether, the polyol and a catalyst are then added. The totalamount of polyether can be divided and added in one or more portions, ascan the catalyst. The polyether is added first and the reaction of theOH end groups of the polyether and of the polyol with the COOH endgroups of the polyamide starts, with the formation of ester linkages andthe elimination of water. Water is removed as much as possible from thereaction mixture by distillation and then the catalyst is introduced inorder to complete the linking of the polyamide blocks to the polyetherblocks. This second step takes place with stirring, preferably under avacuum of at least 50 millibar (5000 Pascals) at a temperature such thatthe reactants and the copolymers obtained are in the molten state. Byway of example, this temperature can be from about 100 to about 400degrees C., such as from about 200 to about 250 degrees C. The reactionis monitored by measuring the torque exerted by the polymer melt on thestirrer or by measuring the electric power consumed by the stirrer. Theend of the reaction is determined by the value of the torque or of thetarget power. The catalyst is defined as being any product whichpromotes the linking of the polyamide blocks to the polyether blocks byesterification. The catalyst can be a derivative of a metal (M) chosenfrom the group formed by titanium, zirconium and hafnium. The derivativecan be prepared from a tetraalkoxides consistent with the generalformula M(OR)4, in which M represents titanium, zirconium or hafnium andR, which can be identical or different, represents linear or branchedalkyl radicals having from 1 to 24 carbon atoms.

The catalyst can comprise a salt of the metal (M), particularly the saltof (M) and of an organic acid and the complex salts of the oxide of (M)and/or the hydroxide of (M) and an organic acid. The organic acid can beformic acid, acetic acid, propionic acid, butyric acid, valeric acid,caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid,cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, maleic acid, fumaric acid, phthalic acid or crotonic acid. Theorganic acid can be an acetic acid or a propionic acid. M can bezirconium and such salts are called zirconyl salts, e.g., thecommercially available product sold under the name zirconyl acetate.

The weight proportion of catalyst can vary from about 0.01 to about 5percent of the weight of the mixture of the dicarboxylic polyamide withthe polyetherdiol and the polyol. The weight proportion of catalyst canvary from about 0.05 to about 2 percent of the weight of the mixture ofthe dicarboxylic polyamide with the polyetherdiol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper andthe polyether are blended together; what is then obtained is a polymerhaving essentially polyether blocks and polyamide blocks of highlyvariable length, but also the various reactants that have reactedrandomly, which are distributed randomly along the polymer chain. Theyare the same reactants and the same catalyst as in the two-step processdescribed above. If the polyamide precursors are only lactams, it isadvantageous to add a little water. The copolymer has essentially thesame polyether blocks and the same polyamide blocks, but also a smallportion of the various reactants that have reacted randomly, which aredistributed randomly along the polymer chain. As in the first step ofthe two-step process described above, the reactor is closed and heated,with stirring. The pressure established is from about 5 to about 30 bar.When the pressure no longer changes, the reactor is put under reducedpressure while still maintaining vigorous stirring of the moltenreactants. The reaction is monitored as previously in the case of thetwo-step process.

The proper ratio of polyamide to polyether blocks can be found in asingle poly(ether block amide), or a blend of two or more differentcomposition poly(ether block amide)s can be used with the proper averagecomposition. It can be useful to blend a block copolymer having a highlevel of polyamide groups with a block copolymer having a higher levelof polyether blocks, to produce a blend having an average level ofpolyether blocks of about 20 to about 40 weight percent of the totalblend of poly(amid-block-ether) copolymers, or about 30 to about 35weight percent. The copolymer can comprise a blend of two differentpoly(ether-block-amide)s comprising at least one block copolymer havinga level of polyether blocks below 35 weight percent, and a secondpoly(ether-block-amide) having at least 45 weight percent of polyetherblocks.

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of “VESTAMID” (EvonikIndustries, Essen, Germany); “PLATAMID” (Arkema, Colombes, France),e.g., product code H2694; “PEBAX” (Arkema), e.g., product code “PEBAXMH1657” and “PEBAX MV1074”; “PEBAX RNEW” (Arkema); “GRILAMID”(EMS-Chemie AG, Domat-Ems, Switzerland), or also to other similarmaterials produced by various other suppliers.

The polyamide can be physically crosslinked through, e.g., nonpolar orpolar interactions between the polyamide groups of the polymers. Inexamples where the polyamide is a copolyamide, the copolyamide can bephysically crosslinked through interactions between the polyamidegroups, and optionally by interactions between the copolymer groups.When the co-polyamide is physically crosslinked through interactionsbetween the polyamide groups, the polyamide segments can form theportion of the polymer referred to as the hard segment, and copolymersegments can form the portion of the polymer referred to as the softsegment. For example, when the copolyamide is a poly(ether-block-amide),the polyamide segments form the hard segments of the polymer, andpolyether segments form the soft segments of the polymer. Therefore, insome examples, the polymer can include a physically crosslinkedpolymeric network having one or more polymer chains with amide linkages.

The polyamide segment of the co-polyamide can include polyamide-11 orpolyamide-12 and the polyether segment can be a segment selected fromthe group consisting of polyethylene oxide, polypropylene oxide, andpolytetramethylene oxide segments, and combinations thereof.

The polyamide can be partially or fully covalently crosslinked, aspreviously described herein. In some cases, the degree of crosslinkingpresent in the polyamide is such that, when it is thermally processed,e.g., in the form of a yarn or fiber to form the articles of the presentdisclosure, the partially covalently crosslinked thermoplastic polyamideretains sufficient thermoplastic character that the partially covalentlycrosslinked thermoplastic polyamide is melted during the processing andre-solidifies. In other cases, the crosslinked polyamide is a thermosetpolymer.

Polyesters

The polymers can comprise a polyester. The polyester can comprise athermoplastic polyester, or a thermoset polyester. Additionally, thepolyester can be an elastomeric polyester, including a thermoplasticpolyester or a thermoset elastomeric polyester. The polyester can beformed by reaction of one or more carboxylic acids, or its ester-formingderivatives, with one or more bivalent or multivalent aliphatic,alicyclic, aromatic or araliphatic alcohols or a bisphenol. Thepolyester can be a polyester homopolymer having repeating polyestersegments of the same chemical structure. Alternatively, the polyestercan comprise a number of polyester segments having different polyesterchemical structures (e.g., polyglycolic acid segments, polylactic acidsegments, polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, etc.). The polyester segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare a polyesterinclude, but are not limited to, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedicarboxylic acid, undecane dicarboxylic acid, terephthalic acid,isophthalic acid, alkyl-substituted or halogenated terephthalic acid,alkyl-substituted or halogenated isophthalic acid, nitro-terephthalicacid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioetherdicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid,4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylicacid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid. Exemplary diols or phenols suitable for the preparation of thepolyester include, but are not limited to, ethylene glycol, diethyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol,2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol,1,4-cyclohexane dimethanol, and bis-phenol A.

The polyester can be a polybutylene terephthalate (PBT), apolytrimethylene terephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), a liquid crystal polyester, or a blendor mixture of two or more of the foregoing.

The polyester can be a co-polyester (i.e., a co-polymer includingpolyester segments and non-polyester segments). The co-polyester can bean aliphatic co-polyester (i.e., a co-polyester in which both thepolyester segments and the non-polyester segments are aliphatic).Alternatively, the co-polyester can include aromatic segments. Thepolyester segments of the co-polyester can comprise or consistessentially of polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, or any combination thereof. The polyestersegments of the co-polyester can be arranged randomly, or can bearranged as repeating blocks.

For example, the polyester can be a block co-polyester having repeatingblocks of polymeric units of the same chemical structure which arerelatively harder (hard segments), and repeating blocks of the samechemical structure which are relatively softer (soft segments). In blockco-polyesters, including block co-polyesters having repeating hardsegments and soft segments, physical crosslinks can be present withinthe blocks or between the blocks or both within and between the blocks.The polymer can comprise or consist essentially of an elastomericco-polyester having repeating blocks of hard segments and repeatingblocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consistessentially of polyether segments, polyamide segments, or both polyethersegments and polyamide segments. The co-polyester can be a blockco-polyester, or can be a random co-polyester. The co-polyester can beformed from the polycondensation of a polyester oligomer or prepolymerwith a second oligomer prepolymer to form a block copolyester.Optionally, the second prepolymer can be a hydrophilic prepolymer. Forexample, the co-polyester can be formed from the polycondensation ofterephthalic acid or naphthalene dicarboxylic acid with ethylene glycol,1,4-butanediol, or 1,3-propanediol. Examples of co-polyesters includepolyethylene adipate, polybutylene succinate,poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenenapthalate, and combinations thereof. The co-polyamide can comprise orconsist of polyethylene terephthalate.

The polyester can be a block copolymer comprising segments of one ormore of polybutylene terephthalate (PBT), a polytrimethyleneterephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), and a liquid crystal polyester. Forexample, a suitable polyester that is a block copolymer can be a PET/PEIcopolymer, a polybutylene terephthalate/tetraethylene glycol copolymer,a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, ora blend or mixture of any of the foregoing.

The polyester can be a biodegradable resin, for example, a copolymerizedpolyester in which poly(α-hydroxy acid) such as polyglycolic acid orpolylactic acid is contained as principal repeating units.

The disclosed polyesters can be prepared by a variety ofpolycondensation methods known to the skilled artisan, such as a solventpolymerization or a melt polymerization process.

Polyolefins

The polymers can comprise or consist essentially of a polyolefin. Thepolyolefin can be a thermoplastic polyolefin or a thermoset polyolefin.Additionally, the polyolefin can be an elastomeric polyolefin, includinga thermoplastic elastomeric polyolefin or a thermoset elastomericpolyolefin. Exemplary polyolefins can include polyethylene,polypropylene, and olefin elastomers (e.g., metallocene-catalyzed blockcopolymers of ethylene and α-olefins having 4 to about 8 carbon atoms).The polyolefin can be a polymer comprising a polyethylene, anethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), apolybutene, a polyisobutylene, a poly-4-methylpent-1-ene, apolyisoprene, a polybutadiene, a ethylene-methacrylic acid copolymer,and an olefin elastomer such as a dynamically cross-linked polymerobtained from polypropylene (PP) and an ethylene-propylene rubber(EPDM), and blends or mixtures of the foregoing. Further exemplarypolyolefins include polymers of cycloolefins such as cyclopentene ornorbornene.

It is to be understood that polyethylene, which optionally can becrosslinked, is inclusive a variety of polyethylenes, including lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE), medium density polyethylene (MDPE), high densitypolyethylene (HDPE), high density and high molecular weight polyethylene(HDPE-HMW), high density and ultrahigh molecular weight polyethylene(HDPE-UHMVV), and blends or mixtures of any the foregoing polyethylenes.A polyethylene can also be a polyethylene copolymer derived frommonomers of monolefins and diolefins copolymerized with a vinyl, acrylicacid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinylacetate. Polyolefin copolymers comprising vinyl acetate-derived unitscan be a high vinyl acetate content copolymer, e.g., greater than about50 weight percent vinyl acetate-derived composition.

The polyolefin can be formed through free radical, cationic, and/oranionic polymerization by methods well known to those skilled in the art(e.g., using a peroxide initiator, heat, and/or light). The disclosedpolyolefin can be prepared by radical polymerization under high pressureand at elevated temperature. Alternatively, the polyolefin can beprepared by catalytic polymerization using a catalyst that normallycontains one or more metals from group IVb, Vb, VIb or VIII metals. Thecatalyst usually has one or more than one ligand, typically oxides,halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/oraryls that can be either p- or s-coordinated complexed with the groupIVb, Vb, VIb or VIII metal. The metal complexes can be in the free formor fixed on substrates, typically on activated magnesium chloride,titanium(III) chloride, alumina or silicon oxide. The metal catalystscan be soluble or insoluble in the polymerization medium. The catalystscan be used by themselves in the polymerization or further activatorscan be used, typically a group Ia, IIa and/or IIIa metal alkyls, metalhydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes.The activators can be modified conveniently with further ester, ether,amine or silyl ether groups.

Suitable polyolefins can be prepared by polymerization of monomers ofmonolefins and diolefins as described herein. Exemplary monomers thatcan be used to prepare the polyolefin include, but are not limited to,ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixturesthereof.

Suitable ethylene-α-olefin copolymers can be obtained bycopolymerization of ethylene with an α-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

Suitable dynamically cross-linked polymers can be obtained bycross-linking a rubber component as a soft segment while at the sametime physically dispersing a hard segment such as PP and a soft segmentsuch as EPDM by using a kneading machine such as a Banbury mixer and abiaxial extruder.

The polyolefin can be a mixture of polyolefins, such as a mixture of twoor more polyolefins disclosed herein above. For example, a suitablemixture of polyolefins can be a mixture of polypropylene withpolyisobutylene, polypropylene with polyethylene (for example PP/HDPE,PP/LDPE) or mixtures of different types of polyethylene (for exampleLDPE/HDPE).

The polyolefin can be a copolymer of suitable monolefin monomers or acopolymer of a suitable monolefin monomer and a vinyl monomer. Exemplarypolyolefin copolymers include ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

The polyolefin can be a polypropylene homopolymer, a polypropylenecopolymers, a polypropylene random copolymer, a polypropylene blockcopolymer, a polyethylene homopolymer, a polyethylene random copolymer,a polyethylene block copolymer, a low density polyethylene (LDPE), alinear low density polyethylene (LLDPE), a medium density polyethylene,a high density polyethylene (HDPE), or blends or mixtures of one or moreof the preceding polymers.

The polyolefin can be a polypropylene. The term “polypropylene,” as usedherein, is intended to encompass any polymeric composition comprisingpropylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as ethylene, butylene, and the like). Such a term also encompassesany different configuration and arrangement of the constituent monomers(such as atactic, syndiotactic, isotactic, and the like). Thus, the termas applied to fibers is intended to encompass actual long strands,tapes, threads, and the like, of drawn polymer. The polypropylene can beof any standard melt flow (by testing); however, standard fiber gradepolypropylene resins possess ranges of Melt Flow Indices between about 1and 1000.

The polyolefin can be a polyethylene. The term “polyethylene,” as usedherein, is intended to encompass any polymeric composition comprisingethylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as propylene, butylene, and the like). Such a term alsoencompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

The thermoplastic and/or thermosetting material can further comprise oneor more processing aids. The processing aid can be a non-polymericmaterial. These processing aids can be independently selected from thegroup including, but not limited to, curing agents, initiators,plasticizers, mold release agents, lubricants, antioxidants, flameretardants, dyes, pigments, reinforcing and non-reinforcing fillers,fiber reinforcements, and light stabilizers.

In articles that include a textile, the primer layer and the opticalelement can be disposed onto the textile. The textile or at least anouter layer of the textile can includes a thermoplastic material thatthe primer layer and the optical element can disposed onto. The textilecan be a nonwoven textile, a synthetic leather, a knit textile, or awoven textile. The textile can comprise a first fiber or a first yarn,where the first fiber or the first yarn can include at least an outerlayer formed of the first thermoplastic material. A region of the firstor second side of the structure onto which the primer layer and theoptical element is disposed can include the first fiber or the firstyarn in a non-filamentous conformation. The optical element can bedisposed onto the textile or the textile can be processed so that theoptical element can be disposed onto the textile. The textured surfacecan be made of or formed from the textile surface. The primer layer canbe disposed on the textile surface and then the optical element can bedisposed onto the primer layer. The textile surface can be used to formthe textured surface, and either before or after this, the primer layercan be optionally applied to the textured surface prior to disposing theoptical element to the textile.

A “textile” may be defined as any material manufactured from fibers,filaments, or yarns characterized by flexibility, fineness, and a highratio of length to thickness. Textiles generally fall into twocategories. The first category includes textiles produced directly fromwebs of filaments or fibers by randomly interlocking to constructnon-woven fabrics and felts. The second category includes textilesformed through a mechanical manipulation of yarn, thereby producing awoven fabric, a knitted fabric, a braided fabric, a crocheted fabric,and the like.

The terms “filament,” “fiber,” or “fibers” as used herein refer tomaterials that are in the form of discrete elongated pieces that aresignificantly longer than they are wide. The fiber can include natural,manmade or synthetic fibers. The fibers may be produced by conventionaltechniques, such as extrusion, electrospinning, interfacialpolymerization, pulling, and the like. The fibers can include carbonfibers, boron fibers, silicon carbide fibers, titania fibers, aluminafibers, quartz fibers, glass fibers, such as E, A, C, ECR, R, S, D, andNE glasses and quartz, or the like. The fibers can be fibers formed fromsynthetic polymers capable of forming fibers such as poly(ether ketone),polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters,polyolefins (e.g., polyethylene, polypropylene), aromatic polyamides(e.g., an aramid polymer such as para-aramid fibers and meta-aramidfibers), aromatic polyimides, polybenzimidazoles, polyetherimides,polytetrafluoroethylene, acrylic, modacrylic, poly(vinyl alcohol),polyamides, polyurethanes, and copolymers such as polyether-polyureacopolymers, polyester-polyurethanes, polyether block amide copolymers,or the like. The fibers can be natural fibers (e.g., silk, wool,cashmere, vicuna, cotton, flax, hemp, jute, sisal). The fibers can beman-made fibers from regenerated natural polymers, such as rayon,lyocell, acetate, triacetate, rubber, and poly(lactic acid).

The fibers can have an indefinite length. For example, man-made andsynthetic fibers are generally extruded in substantially continuousstrands. Alternatively, the fibers can be staple fibers, such as, forexample, cotton fibers or extruded synthetic polymer fibers can be cutto form staple fibers of relatively uniform length. The staple fiber canhave a have a length of about 1 millimeter to 100 centimeters or more aswell as any increment therein (e.g., 1 millimeter increments).

The fiber can have any of a variety of cross-sectional shapes. Naturalfibers can have a natural cross-section, or can have a modifiedcross-sectional shape (e.g., with processes such as mercerization).Man-made or synthetic fibers can be extruded to provide a strand havinga predetermined cross-sectional shape. The cross-sectional shape of afiber can affect its properties, such as its softness, luster, andwicking ability. The fibers can have round or essentially round crosssections. Alternatively, the fibers can have non-round cross sections,such as flat, oval, octagonal, rectangular, wedge-shaped, triangular,dog-bone, multi-lobal, multi-channel, hollow, core-shell, or othershapes.

The fiber can be processed. For example, the properties of fibers can beaffected, at least in part, by processes such as drawing (stretching)the fibers, annealing (hardening) the fibers, and/or crimping ortexturizing the fibers.

In some cases a fiber can be a multi-component fiber, such as onecomprising two or more co-extruded polymeric materials. The two or moreco-extruded polymeric materials can be extruded in a core-sheath,islands-in-the-sea, segmented-pie, striped, or side-by-sideconfiguration. A multi-component fiber can be processed in order to forma plurality of smaller fibers (e.g., microfibers) from a single fiber,for example, by remove a sacrificial material.

The fiber can be a carbon fiber such as TARIFYL produced by FormosaPlastics Corp. of Kaohsiung City, Taiwan, (e.g., 12,000, 24,000, and48,000 fiber tows, specifically fiber types TC-35 and TC-35R), carbonfiber produced by SGL Group of Wiesbaden, Germany (e.g., 50,000 fibertow), carbon fiber produced by Hyosung of Seoul, South Korea, carbonfiber produced by Toho Tenax of Tokyo, Japan, fiberglass produced byJushi Group Co., LTD of Zhejiang, China (e.g., E6, 318, silane-basedsizing, filament diameters 14, 15, 17, 21,and 24 micrometers), andpolyester fibers produced by Amann Group of Bonningheim, Germany (e.g.,SERAFILE 200/2 non-lubricated polyester filament and SERAFILE COMPHIL200/2 lubricated polyester filament).

A plurality of fibers includes 2 to hundreds or thousands or morefibers. The plurality of fibers can be in the form of bundles of strandsof fibers, referred to as tows, or in the form of relatively alignedstaple fibers referred to as sliver and roving. A single type fiber canbe used either alone or in combination with one or more different typesof fibers by co-mingling two or more types of fibers. Examples ofco-mingled fibers include polyester fibers with cotton fibers, glassfibers with carbon fibers, carbon fibers with aromatic polyimide(aramid) fibers, and aromatic polyimide fibers with glass fibers.

As used herein, the term “yarn” refers to an assembly formed of one ormore fibers, wherein the strand has a substantial length and arelatively small cross-section, and is suitable for use in theproduction of textiles by hand or by machine, including textiles madeusing weaving, knitting, crocheting, braiding, sewing, embroidery, orrope making techniques. Thread is a type of yarn commonly used forsewing.

Yarns can be made using fibers formed of natural, man-made and syntheticmaterials. Synthetic fibers are most commonly used to make spun yarnsfrom staple fibers, and filament yarns. Spun yarn is made by arrangingand twisting staple fibers together to make a cohesive strand. Theprocess of forming a yarn from staple fibers typically includes cardingand drawing the fibers to form sliver, drawing out and twisting thesliver to form roving, and spinning the roving to form a strand.Multiple strands can be plied (twisted together) to make a thicker yarn.The twist direction of the staple fibers and of the plies can affect thefinal properties of the yarn. A filament yarn can be formed of a singlelong, substantially continuous filament, which is conventionallyreferred to as a “monofilament yarn,” or a plurality of individualfilaments grouped together. A filament yarn can also be formed of two ormore long, substantially continuous filaments which are grouped togetherby grouping the filaments together by twisting them or entangling themor both. As with staple yarns, multiple strands can be plied together toform a thicker yarn.

Once formed, the yarn can undergo further treatment such as texturizing,thermal or mechanical treating, or coating with a material such as asynthetic polymer. The fibers, yarns, or textiles, or any combinationthereof, used in the disclosed articles can be sized. Sized fibers,yarns, and/or textiles are coated on at least part of their surface witha sizing composition selected to change the absorption or wearcharacteristics, or for compatibility with other materials. The sizingcomposition facilitates wet-out and wet-through of the coating or resinupon the surface and assists in attaining desired physical properties inthe final article. An exemplary sizing composition can comprise, forexample, epoxy polymers, urethane-modified epoxy polymers, polyesterpolymers, phenol polymers, polyamide polymers, polyurethane polymers,polycarbonate polymers, polyetherimide polymers, polyamideimidepolymers, polystylylpyridine polymers, polyimide polymers bismaleimidepolymers, polysulfone polymers, polyethersulfone polymers,epoxy-modified urethane polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone polymers, and mixtures thereof.

Two or more yarns can be combined, for example, to form composite yarnssuch as single- or double-covered yarns, and corespun yarns.Accordingly, yarns may have a variety of configurations that generallyconform to the descriptions provided herein.

The yarn can comprise at least one thermoplastic material (e.g., one ormore of the fibers can be made of thermoplastic material). The yarn canbe made of a thermoplastic material. The yarn can be coated with a layerof a material such as a thermoplastic material.

The linear mass density or weight per unit length of a yarn can beexpressed using various units, including denier (D) and tex. Denier isthe mass in grams of 9000 meters of yarn. The linear mass density of asingle filament of a fiber can also be expressed using denier perfilament (DPF). Tex is the mass in grams of a 1000 meters of yarn.Decitex is another measure of linear mass, and is the mass in grams fora 10,000 meters of yarn.

As used herein, tenacity is understood to refer to the amount of force(expressed in units of weight, for example: pounds, grams, centinewtonsor other units) needed to break a yarn (i.e., the breaking force orbreaking point of the yarn), divided by the linear mass density of theyarn expressed, for example, in (unstrained) denier, decitex, or someother measure of weight per unit length. The breaking force of the yarnis determined by subjecting a sample of the yarn to a known amount offorce, for example, using a strain gauge load cell such as an INSTRONbrand testing system (Norwood, Mass., USA). Yarn tenacity and yarnbreaking force are distinct from burst strength or bursting strength ofa textile, which is a measure of how much pressure can be applied to thesurface of a textile before the surface bursts.

Generally, in order for a yarn to withstand the forces applied in anindustrial knitting machine, the minimum tenacity required isapproximately 1.5 grams per Denier. Most yarns formed from commoditypolymeric materials generally have tenacities in the range of about 1.5grams per Denier to about 4 grams per Denier. For example, polyesteryarns commonly used in the manufacture of knit uppers for footwear havetenacities in the range of about 2.5 to about 4 grams per Denier. Yarnsformed from commodity polymeric materials which are considered to havehigh tenacities generally have tenacities in the range of about 5 gramsper Denier to about 10 grams per Denier. For example, commerciallyavailable package dyed polyethylene terephthalate yarn from NationalSpinning (Washington, N.C., USA) has a tenacity of about 6 grams perDenier, and commercially available solution dyed polyethyleneterephthalate yarn from Far Eastern New Century (Taipei, Taiwan) has atenacity of about 7 grams per Denier. Yarns formed from high performancepolymeric materials generally have tenacities of about 11 grams perDenier or greater. For example, yarns formed of aramid fiber typicallyhave tenacities of about 20 grams per Denier, and yarns formed ofultra-high molecular weight polyethylene (UHMWPE) having tenacitiesgreater than 30 grams per Denier are available from Dyneema (Stanley,N.C., USA) and Spectra (Honeywell-Spectra, Colonial Heights, Va., USA).

Various techniques exist for mechanically manipulating yarns to form atextile. Such techniques include, for example, interweaving,intertwining and twisting, and interlooping. Interweaving is theintersection of two yarns that cross and interweave at right angles toeach other. The yarns utilized in interweaving are conventionallyreferred to as “warp” and “weft.” A woven textile includes include awarp yarn and a weft yarn. The warp yarn extends in a first direction,and the weft strand extends in a second direction that is substantiallyperpendicular to the first direction. Intertwining and twistingencompasses various procedures, such as braiding and knotting, whereyarns intertwine with each other to form a textile. Interloopinginvolves the formation of a plurality of columns of intermeshed loops,with knitting being the most common method of interlooping. The textilemay be primarily formed from one or more yarns that aremechanically-manipulated, for example, through interweaving,intertwining and twisting, and/or interlooping processes, as mentionedabove.

The textile can be a nonwoven textile. Generally, a nonwoven textile orfabric is a sheet or web structure made from fibers and/or yarns thatare bonded together. The bond can be a chemical and/or mechanical bond,and can be formed using heat, solvent, adhesive or a combinationthereof. Exemplary nonwoven fabrics are flat or tufted porous sheetsthat are made directly from separate fibers, molten plastic and/orplastic film. They are not made by weaving or knitting and do notnecessarily require converting the fibers to yarn, although yarns can beused as a source of the fibers. Nonwoven textiles are typicallymanufactured by putting small fibers together in the form of a sheet orweb (similar to paper on a paper machine), and then binding them eithermechanically (as in the case of felt, by interlocking them with serratedor barbed needles, or hydro-entanglement such that the inter-fiberfriction results in a stronger fabric), with an adhesive, or thermally(by applying binder (in the form of powder, paste, or polymer melt) andmelting the binder onto the web by increasing temperature). A nonwoventextile can be made from staple fibers (e.g., from wetlaid, airlaid,carding/crosslapping processes), or extruded fibers (e.g., frommeltblown or spunbond processes, or a combination thereof), or acombination thereof. Bonding of the fibers in the nonwoven textile canbe achieved with thermal bonding (with or without calendering),hydro-entanglement, ultrasonic bonding, needlepunching (needlefelting),chemical bonding (e.g., using binders such as latex emulsions orsolution polymers or binder fibers or powders), meltblown bonding (e.g.,fiber is bonded as air attenuated fibers intertangle during simultaneousfiber and web formation).

Now having described various aspects of the present disclosure,additional discussion is provided regarding when the primer layer isused in conjunction with a bladder. The bladder can be unfilled,partially inflated, or fully inflated when the structural design (e.g.,optical layer structure) is disposed onto the bladder. The bladder is abladder capable of including a volume of a fluid. An unfilled bladder isa fluid-fillable bladder and a filled bladder that has been at leastpartially inflated with a fluid at a pressure equal to or greater thanatmospheric pressure. When disposed onto or incorporated into an articleof footwear, apparel, or sports equipment, the bladder is generally, atthat point, a fluid-filled bladder. The fluid be a gas or a liquid. Thegas can include air, nitrogen gas (N₂), or other appropriate gas.

The bladder can have a gas transmission rate for nitrogen gas, forexample, where a bladder wall of a given thickness has a gastransmission rate for nitrogen that is at least about ten times lowerthan the gas transmission rate for nitrogen of a butyl rubber layer ofsubstantially the same thickness as the thickness of the bladderdescribed herein. The bladder can have a first bladder wall having afirst bladder wall thickness (e.g., about 0.1 to 40 mils). The bladdercan have a first bladder wall that can have a gas transmission rate(GTR) for nitrogen gas of less than about 15 cm³/m²⋅atm⋅day, less thanabout 10 m³/m²⋅atm⋅day, less than about 5 cm³/m²⋅atm⋅day, less thanabout 1 cm³/m²⋅atm⋅day (e.g., from about 0.001 cm³/m²⋅atm⋅day to about 1cm³/m²⋅atm⋅day, about 0.01 cm³/m²⋅atm⋅day to about 1 cm³/m²⋅atm⋅day orabout 0.1 cm³/m²⋅atm⋅day to about 1 cm³/m²⋅atm⋅day) for an average wallthickness of 20 mils. The bladder can have a first bladder wall having afirst bladder wall thickness, where the first bladder wall has a gastransmission rate of 15 cm³/m²⋅atm⋅day or less for nitrogen for anaverage wall thickness of 20 mils.

In an aspect, the bladder has a bladder wall having an interior-facingside and an exterior(or externally)-facing side, where the interior(orinternally)-facing side defines at least a portion of an interior regionof the bladder. The multi-layer optical film (or optical element) havinga first side and a second opposing side can be disposed on theexterior-facing side of the bladder, the interior-facing side of thebladder, or both. The exterior-facing side of the bladder, theinterior-facing side of the bladder, or both can include a plurality oftopographical structures (or profile features) extending from theexterior-facing side of the bladder wall, the interior-facing side ofthe bladder, or both, where the first side or the second side of themulti-layer optical film is disposed on the exterior-facing side of thebladder wall and covering the plurality of topographical structures, theinterior-facing side of the bladder wall and covering the plurality oftopographical structures, or both, and wherein the multi-layer opticalfilm imparts a structural color to the bladder wall. The primer layercan be disposed on the exterior-facing side of the bladder, theinterior-facing side of the bladder, or both, between the bladder walland the multi-layer optical film.

In a particular aspect, the bladder can include a top wall operablysecured to the footwear upper, a bottom wall opposite the top wall, andone or more sidewalls extending between the top wall and the bottom wallof the inflated bladder. The top wall, the bottom wall, and the one ormore sidewalls collectively define an interior region of the inflatedbladder, and wherein the one or more sidewalls each comprise anexterior-facing side. The multi-layer optical film having a first sideand a second opposing side can be disposed on the exterior-facing sideof the bladder, the interior-facing side of the bladder, or both. Theexterior-facing side of the bladder, the interior-facing side of thebladder, or both can include a plurality of topographical structuresextending from the exterior-facing side of the bladder wall, theinterior-facing side of the bladder, or both, where the first side orthe second side of the multi-layer optical film is disposed on theexterior-facing side of the bladder wall and covering the plurality oftopographical structures, the interior-facing side of the bladder walland covering the plurality of topographical structures, or both, andwherein the multi-layer optical film imparts a structural color to thebladder wall. The primer layer can be disposed on the exterior-facingside of the bladder, the interior-facing side of the bladder, or both,between the bladder wall and the multi-layer optical film.

An accepted method for measuring the relative permeance, permeability,and diffusion of inflated bladders is ASTM D-1434-82-V. See, e.g., U.S.Pat. No. 6,127,026, which is incorporated by reference as if fully setforth herein. According to ASTM D-1434-82-V, permeance, permeability anddiffusion are measured by the following formulae:

Permeance

(quantity of gas)/[(area)×(time)×(pressure difference)]=permeance(GTR)/(pressure difference)=cm³/m²⋅atm⋅day (i.e., 24 hours)

Permeability

[(quantity of gas)×(film thickness)][(area)×(time)×(pressuredifference)]=permeability [(GTR)×(film thickness)]/(pressuredifference)=[(cm³)(mil)]/m²⋅atm⋅day (i.e., 24 hours)

Diffusion at One Atmosphere

(quantity of gas)/[(area)×(time)]=GTR=cm³/m²⋅day (i.e., 24 hours)

The bladder can include a bladder wall that includes a film including atleast one polymeric layer or at least two or more polymeric layers. Eachof the polymeric layers can be about 0.1 to 40 mils in thickness.

The polymeric layer can be formed of polymer material such as athermoplastic material as described above and herein and can be thethermoplastic layer upon which the primer layer, the optical element canbe disposed, upon which the textured layer can be disposed, can be usedto form the textured layer, and the like. The thermoplastic material caninclude an elastomeric material, such as a thermoplastic elastomericmaterial. The thermoplastic materials can include thermoplasticpolyurethane (TPU), such as those described above and herein. Thethermoplastic materials can include polyester-based TPU, polyether-basedTPU, polycaprolactone-based TPU, polycarbonate-based TPU,polysiloxane-based TPU, or combinations thereof. Non-limiting examplesof thermoplastic material that can be used include: “PELLETHANE”2355-85ATP and 2355-95AE (Dow Chemical Company of Midland, Mich., USA),“ELASTOLLAN” (BASF Corporation, Wyandotte, Mich., USA) and “ESTANE”(Lubrizol, Brecksville, Ohio, USA), all of which are either ester orether based. Additional thermoplastic material can include thosedescribed in U.S. Pat. Nos. 5,713,141; 5,952,065; 6,082,025; 6,127,026;6,013,340; 6,203,868; and 6,321,465, which are incorporated herein byreference.

The polymeric layer can be formed of one or more of the following:ethylene-vinyl alcohol copolymers (EVOH), poly(vinyl chloride),polyvinylidene polymers and copolymers (e.g., polyvinylidene chloride),polyamides (e.g., amorphous polyamides), acrylonitrile polymers (e.g.,acrylonitrile-methyl acrylate copolymers), polyurethane engineeringplastics, polymethylpentene resins, ethylene-carbon monoxide copolymers,liquid crystal polymers, polyethylene terephthalate, polyether imides,polyacrylic imides, and other polymeric materials known to haverelatively low gas transmission rates. Blends and alloys of thesematerials as well as with the TPUs described herein and optionallyincluding combinations of polyimides and crystalline polymers, are alsosuitable. For instance, blends of polyimides and liquid crystalpolymers, blends of polyamides and polyethylene terephthalate, andblends of polyamides with styrenics are suitable.

Specific examples of polymeric materials of the polymeric layer caninclude acrylonitrile copolymers such as “BAREX” resins, available fromIneos (Rolle, Switzerland); polyurethane engineering plastics such as“ISPLAST” ETPU available from Lubrizol (Brecksville, Ohio, USA);ethylene-vinyl alcohol copolymers marketed under the tradenames “EVAL”by Kuraray (Houston, Tex., USA), “SOARNOL” by Nippon Gohsei (Hull,England), and “SELAR OH” by DuPont (Wilmington, Del., USA);polyvinylidiene chloride available from S.C. Johnson (Racine, Wis., USA)under the tradename “SARAN”, and from Solvay (Brussels, Belgium) underthe tradename “IXAN”; liquid crystal polymers such as “VECTRA” fromCelanese (Irving, Tex., USA) and “XYDAR” from Solvay; “MDX6” nylon, andamorphous nylons such as “NOVAMID” X21 from Koninklijke DSM N.V(Heerlen, Netherlands), “SELAR PA” from DuPont; polyetherimides soldunder the tradename “ULTEM” by SABIC (Riyadh, Saudi Arabia); poly(vinylalcohol)s; and polymethylpentene resins available from Mitsui Chemicals(Tokyo, Japan) under the tradename “TPX”.

Each polymeric layer of the film can be formed of a thermoplasticmaterial which can include a combination of thermoplastic polymers. Inaddition to one or more thermoplastic polymers, the thermoplasticmaterial can optionally include a colorant, a filler, a processing aid,a free radical scavenger, an ultraviolet light absorber, and the like.Each polymeric layer of the film can be made of a different ofthermoplastic material including a different type of thermoplasticpolymer.

The bladder can be made by applying heat, pressure and/or vacuum to afilm. In this regard, the primer layer, the optical element, thetextured layer, and the like can be disposed, formed from, or the likeprior to, during, and/or after these steps. The bladder (e.g., one ormore polymeric layers) can be formed using one or more polymericmaterials, and forming the bladder using one or more processingtechniques including, for example, extrusion, blow molding, injectionmolding, vacuum molding, rotary molding, transfer molding, pressureforming, heat sealing, casting, low-pressure casting, spin casting,reaction injection molding, radio frequency (RF) welding, and the like.The bladder can be made by co-extrusion followed by heat sealing orwelding to give an inflatable bladder, which can optionally include oneor more valves (e.g., one way valves) that allows the bladder to befilled with the fluid (e.g., gas).

Now having described the the primer layer, the optical element, theoptional textured surface, and methods of making the article are nowdescribed. In an aspect, the method includes forming the primer layerhaving a percent transmittance of about 40% or less, about 30% or less,about 20% or less, or about 10% or less. In an aspect, the methodincludes forming the primer layer on a surface of an article such as atextile, film, fiber, or monofilament yarn, where the surface canoptionally be the textured surface. The primer layer can be formed usingone or more techniques including digital printing, offset printing, padprinting, screen printing, flexographic printing, or heat transferprinting.

The method provides for the primer layer being formed on the texturedsurface. Subsequently, the optical element can be disposed on the primerlayer. Alternatively, the textured surface can be formed on the primerlayer, and then the optical element is disposed on the textured surface.As described herein, the optical element can be formed in alayer-by-layer manner over the textured surface, where each layer has adifferent index of refraction. As each layer is formed the undulationsand flat regions are altered. The combination of the primer layer, theoptional textured surface (e.g., dimensions, shape, and/or spacing ofthe profile elements) and the optical element (e.g., number of layers,thickness of layers, material of the layers) and the resultantundulations and planar areas impart the structural color when exposed tovisible light. The method includes optionally forming a protective layerover the optical element to protect the optical element.

Another embodiment of the present disclosure includes providing primerlayer having a percent transmittance of 40 percent or less and thetextured surface on the substrate, where the primer layer can bedisposed on the textured surface or the textured surface can be disposedon the primer layer. A second device can be configured to form opticalelement on the textured surface of the texture layer or the primerlayer. Each layer of the optical element can be formed in turn, whereeach layer can be formed then after an appropriate amount of time,additional processing, cooling, or the like, the next layer of theoptical element can be formed.

It should be emphasized that the above-described aspects of the presentdisclosure are merely possible examples of implementations, and are setforth only for a clear understanding of the principles of thedisclosure. Many variations and modifications may be made to theabove-described aspects of the disclosure without departingsubstantially from the spirit and principles of the disclosure. All suchmodifications and variations are intended to be included herein withinthe scope of this disclosure.

The present disclosure can be described in accordance with the followingClauses, which should not be confused with the claims. The word“disposing” can be replaced with “operably disposing” in each of theclauses.

Clause 1. A method, comprising:

forming a primer layer having a percent transmittance of about 40% orless; and

forming an optical element on a top surface of the primer layer, whereinthe primer layer, and the optical element impart a structural color.

Clause 2. The method of clause 1, wherein forming the primer layercomprises forming the primer layer on a surface of an article.Clause 3. The method of any one of the preceding clauses, whereinforming the primer layer comprises using: digital printing, offsetprinting, pad printing, screen printing, flexographic printing, or heattransfer printing.Clause 4. The method of any one of the preceding clauses, wherein thematrix of crosslinked polymers or the dispersion of polymers of thecoating include polyurethane polymers.Clause 5. The method of any of the previous method clauses, wherein thearticle is an article according to any one of the article clauses.Clause 6. An article comprising: a product of the method of any one ofthe preceding clauses.Clause 7. An article comprising:

a primer layer having a percent transmittance of about 40 percent orless and an optical element, wherein the primer layer and the opticalelement impart a structural color to the article.

Clause 8. The article of clause 7, wherein the primer layer furthercomprises a textured surface, and the textured surface of the primerlayer, the primer layer, and the optical element impart the structuralcolor.Clause 9. The article of any one of the preceding clauses, wherein thesurface of the article is a textured surface, wherein the primer layeris on the textured surface, and the textured surface of the substrate,the primer layer, and the optical element impart the structural color.Clause 10. The article of any one of the preceding clauses, wherein theprimer layer is disposed between the optical element and the surface ofthe article.Clause 11. The article of any one of the preceding clauses, wherein thetextured surface is present, and the primer layer is disposed betweenthe textured surface and the optical elementClause 12. The article of any one of the preceding clauses, wherein theoptical element is disposed on a first polymeric material defining thesurface of the article, with the primer layer, the textured surface, orboth, positioned between the optical element and the first polymericmaterial.Clause 13. The article of any one of the preceding clauses, wherein theprimer layer comprises a paint, an ink, a reground, and at leastpartially degraded polymer.Clause 14. The article of any one of the preceding clauses, wherein theprimer layer consists essentially of one or more doped metal oxides, oneor more doped metal oxynitrides, or a combination of one or more dopedmetal oxides and one or more doped metal oxynitrides.Clause 15. The article of any one of the preceding clauses, wherein theprimer layer is a coating, and the coating is a crosslinked coatingincluding a matrix of crosslinked polymers.Clause 16. The article of any one of the preceding clauses, wherein thecoating comprises a plurality of solid pigment particles entrapped inthe matrix of crosslinked polymers.Clause 17. The article of any one of the preceding clauses, wherein thematrix of crosslinked polymers includes crosslinked elastomericpolymers, optionally wherein the crosslinked elastomeric polymersinclude crosslinked polyurethane homopolymers or copolymers or both, oroptionally wherein the crosslinked polyurethane copolymers includecrosslinked polyester polyurethanes.Clause 18. The article of any one of the preceding clauses, wherein theprimer layer is a coating, wherein the coating is a product ofcrosslinking a polymeric coating composition, the polymeric coatingcomposition comprises a dispersion of polymers, optionally wherein thedispersion of polymers is a water-borne dispersion of polymers.Clause 19. The article of any one of the preceding clauses, wherein thepolymeric coating composition further comprises a crosslinking agent,optionally wherein the crosslinking agent is a water-borne crosslinkingagent.Clause 20. The article of any one of the preceding clauses, wherein thepolymeric coating composition further comprises a plurality of solidpigment particles mixed with the dispersion of polymers.Clause 21. The article of any one of the preceding clauses, wherein thepolymeric coating composition further comprises a solubilized dye.Clause 22. The article of any one of the preceding clauses, wherein thepolymeric coating composition further comprises an organic solvent,optionally wherein the organic solvent is a water-miscible organicsolvent.Clause 23. The article of any one of the preceding clauses, wherein thecoating further comprises a dye.Clause 24. The article of any one of the preceding clauses, wherein,when the solid pigment particles are present, the solid pigmentparticles are selected from the group consisting of: metal and metaloxide pigments, carbon pigments, clay earth pigments, ultramarinepigments and a combination thereof.Clause 25. The article of any one of the preceding clauses, wherein,when the dye is present, the dye is an acid dye.Clause 26. The article of any one of the preceding clauses, wherein thecoating further comprises a quaternary ammonium compound, optionallywherein the quaternary ammonium compound is a tetrabutyl ammoniumcompound, optionally wherein the tetraalkyl ammonium compound is atetrabutyl ammonium halide, optionally wherein the polymeric coatingcomposition, when present, comprises 1-15 weight percent of thequaternary ammonium compound, optionally wherein a molar ratio of theacid dye to the quaternary ammonium compound ranges from 3:1 to 1:3, oroptionally wherein the molar ratio of the acid dye to the quaternaryammonium compound ranges from about 1.5:1 to 1:1.5.Clause 27. The article of any one of the preceding clauses, wherein thepolyurethane polymers include thermoplastic polyurethane polymers,optionally wherein the polyurethane polymers include elastomericpolyurethane polymers, optionally wherein the polyurethane polymersinclude polyester polyurethane copolymers, or optionally wherein thepolyurethane polymers consist essentially of polyester polyurethanecopolymers.Clause 28. The article of any one of the preceding clauses, wherein theprimer layer has a thickness of about 3 nanometers to about 200nanometers.Clause 29. The article of any one of the preceding clauses, wherein theprimer layer has a color selected from the group consisting of: black,dark brown, dark red, dark orange, dark yellow, dark green, dark cyan,dark blue, dark violet, grey, dark magenta, dark indigo, tones thereof,tints thereof, shades thereof, and a combination thereof.Clause 30. The article of any one of the proceeding clauses, wherein theoptical element, as disposed onto the article, when measured accordingto the CIE 1976 color space under a given illumination condition atthree observation angles between −15 degrees and +60 degrees, has afirst color measurement at a first angle of observation havingcoordinates L₁* and a₁* and b₁*, and a second color measurement at asecond angle of observation having coordinates L₂* and a₂* and b₂*, anda third color measurement at a third angle of observation havingcoordinates L₃* and a₃* and b₃*, wherein the L₁*, L₂*, and L₃* valuesmay be the same or different, wherein the a₁*, a₂*, and a₃* coordinatevalues may be the same or different, wherein the b₁*, b₂*, and b₃*coordinate values may be the same or different, and wherein the range ofthe combined a₁*, a₂* and a₃* values is less than about 40% of theoverall scale of possible a* values, or optionally wherein the range ofthe combined a₁*, a₂* and a₃* values is less than about 30% of theoverall scale of possible a* values, or optionally wherein the range ofthe combined a₁*, a₂* and a₃* values is less than about 20% of theoverall scale of possible a* values, or optionally, wherein the range ofthe combined a₁*, a₂* and a₃* values is less than about 10% of theoverall scale of possible a* values.Clause 31. The article of any one of the proceeding clauses, wherein theoptical element, as disposed onto the article, when measured accordingto the CIE 1976 color space under a given illumination condition atthree observation angles between −15 degrees and +60 degrees, has afirst color measurement at a first angle of observation havingcoordinates L₁* and a₁* and b₁*, and a second color measurement at asecond angle of observation having coordinates L₂* and a₂* and b₂*, anda third color measurement at a third angle of observation havingcoordinates L₃* and a₃* and b₃*, wherein the L₁*, L₂*, and L₃* valuesmay be the same or different, wherein the a₁*, a₂*, and a₃* coordinatevalues may be the same or different, wherein the b₁*, b₂*, and b₃*coordinate values may be the same or different, and wherein the range ofthe combined b₁*, b₂* and b₃* values is less than about 40% of theoverall scale of possible b* values or optionally wherein the range ofthe combined b₁*, b₂* and b₃* values is less than about 30% of theoverall scale of possible b* values, or optionally wherein the range ofthe combined b₁*, b₂* and b₃* values is less than about 20% of theoverall scale of possible b* values, or optionally wherein the range ofthe combined b₁*, b₂* and b₃* values is less than about 10% of theoverall scale of possible b* values.Clause 32. The article of any one of the proceeding clauses, wherein theoptical element, as disposed onto to the article, when measuredaccording to the CIE 1976 color space under a given illuminationcondition at two observation angles between −15 degrees and +60 degrees,has a first color measurement at a first angle of observation havingcoordinates L₁* and a₁* and b₁*, and a second color measurement at asecond angle of observation having coordinates L₂* and a2* and b₂*,wherein the L₁* and L₂* values may be the same or different, wherein thea₁* and a₂* coordinate values may be the same or different, wherein theb₁* and b₂* coordinate values may be the same or different, and whereinthe ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 100, whereΔE*ab=[(L₁*−L₂*)²+(a¹*−a₂*)+(b₁*−b₂*)²]^(1/2), or optionally wherein theΔE*ab between the first color measurement and the second colormeasurement is less than or equal to about 80, or optionally wherein theΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 60.Clause 33. The article of any one of the proceeding clauses, wherein theoptical element, as disposed onto to the article, when measuredaccording to the CIELCH color space under a given illumination conditionat three observation angles between −15 degrees and +60 degrees, has afirst color measurement at a first angle of observation havingcoordinates L₁* and C₁* and h₁°, and a second color measurement at asecond angle of observation having coordinates L₂* and C₂* and h₂°, anda third color measurement at a third angle of observation havingcoordinates L₃* and C₃* and h₃°, wherein the L₁*, L₂*, and L₃* valuesmay be the same or different, wherein the C₁*, C₂*, and C₃* coordinatevalues may be the same or different, wherein the h₁°, h₂° and h₃°coordinate values may be the same or different, and wherein the range ofthe combined h₁°, h₂° and h₃° values is less than about 60 degrees, oroptionally wherein the range of the combined h₁°, h₂° and h₃° values isless than about 50 degrees, or optionally wherein the range of thecombined h₁°, h₂° and h₃° values is less than about 40 degrees, oroptionally wherein the range of the combined h₁°, h₂° and h₃° values isless than about 30 degrees, or optionally wherein the range of thecombined h₁°, h₂° and h₃° values is less than about 20 degrees.Clause 34. The article of any one of the preceding clauses, wherein thecolor of the primer layer is different than the color of the structuralcolor, optionally wherein the color of the primer layer differs from thecolor imparted by the structural color by at least one of hue, value andiridescence type.Clause 35. The article of any one of the proceeding clauses, wherein thecolor of the primer layer is different than the color of the structuralcolor under the criteria in preceding clauses.Clause 36. The article of any one of the preceding clauses, wherein thetextured surface includes a plurality of profile features and flatplanar areas, wherein the profile features extend above the flat areasof the textured surface, optionally wherein the dimensions of theprofile features, a shape of the profile features, a spacing among theplurality of the profile features, in combination with the opticalelement create the structural color, optionally wherein the profilefeatures are in random positions relative to one another for a specificarea, optionally wherein the spacing among the profile features is setto reduce distortion effects of the profile features from interferingwith one another in regard to the structural color of the article,optionally wherein the profile features and the flat areas result in atleast one layer of the optical element having an undulating topographyacross the textured surface, wherein there is a planar region betweenneighboring profile features that is planar with the flat planar areasof the textured surface, wherein the planar region has dimensionsrelative to the profile features to impart the structural color,optionally wherein the profile features and the flat areas result ineach layer of the optical element having an undulating topography acrossthe textured surface.Clause 37. The article of any one of the preceding clauses, wherein theoptical element is a multilayer reflector or a multilayer filter,optionally wherein the multilayer reflector has at least two layers,wherein adjacent layer have different refractive indices, optionallywherein the each layer of the multilayer reflector has a thickness ofabout one quarter of the wavelength of the wavelength to be reflected.Clause 38. The article of any one of the preceding clauses, wherein theeach layer of the multilayer reflector is made of a material selectedfrom the group consisting of: silicon dioxide, titanium dioxide, zincsulphide, magnesium fluoride, tantalum pentoxide, and a combinationthereof.Clause 39. The article of any one of the preceding clauses, wherein thestructural color exhibits a single hue or multiple different hues whenviewed from different viewing angles at least 15 degrees apart.Clause 40. The article of any one of the preceding clauses, wherein thesurface of the article is a textured surface, and the textured surfaceis is defined by a thermoplastic material.Clause 41. The article of any one of the preceding clauses, wherein thesurface of the article is a textured surface, and the textured surfaceis defined by a partially cured or cured material layer.Clause 42. The article of any one of the preceding clauses, wherein theprimer layer is substantially free of pigments, dyes, and a combinationthereof.Clause 43. The article of any one of the preceding clauses, wherein theprimer layer includes a red pigment, red dye, or a combination thereof.Clause 44. The article of any one of the preceding clauses, wherein theprimer layer includes a black pigment, black dye, or a combinationthereof.Clause 45. The article of any one of the preceding clauses, wherein thearticle is a fiber.Clause 46. The article of any one of the preceding clauses, wherein thearticle is a yarn.Clause 82. The article of any one of the preceding clauses, wherein thearticle is a monofilament yarn.Clause 47. The article of any one of the preceding clauses, wherein thearticle is a textile.Clause 48. The article of any one of the preceding clauses, wherein thearticle is a knit textile.Clause 49. The article of any one of the preceding clauses, wherein thearticle is a non-woven textile.Clause 50. The article of any one of the preceding clauses, wherein thearticle is a non-woven synthetic leather.Clause 51. The article of any one of the preceding clauses, wherein thearticle is a film.Clause 52. The article of any one of the preceding clauses, wherein thearticle is an article of footwear, a component of footwear, an articleof apparel, a component of apparel, an article of sporting equipment, ora component of sporting equipment.Clause 53. The article of any one of the preceding clauses, wherein thearticle is an article of footwear.Clause 54. The article of any one of the preceding clauses, wherein thearticle is a sole component of an article of footwear.Clause 55. The article of any one of the preceding clauses, wherein thearticle is foam midsole component of an article of footwear.Clause 56. The article of any one of the preceding clauses, wherein thearticle is an upper component of an article of footwear.Clause 57. The article of any one of the preceding clauses, wherein thearticle is a knit upper component of an article of footwear.Clause 58. The article of any one of the preceding clauses, wherein thearticle is a non-woven synthetic leather upper for an article offootwear.Clause 59. The article of any one of the preceding clauses, wherein thearticle is a bladder including a volume of a fluid, wherein the bladderhas a first bladder wall having a first bladder wall thickness, whereinthe first bladder wall has a gas transmission rate of 15 cm³/m²⋅atm⋅dayor less for nitrogen for an average wall thickness of 20 mils.Clause 60. The article of any one of the preceding clauses, wherein thearticle is a bladder, and the primer layer is optionally on an insidesurface of the bladder or optionally the primer layer is on an outsidesurface of the bladder.Clause 61. The article of any preceding clause, wherein the structuralcolor is visible to a viewer having 20/20 visual acuity and normal colorvision from a distance of about 1 meter from the bladder.Clause 62. The article of any preceding clause, wherein the structuralcolor has a single hue.Clause 63. The article of any preceding clause, wherein the structuralcolor includes two or more hues.Clause 64. The article of any preceding clause, wherein the structuralcolor is iridescent.Clause 65. The article of any preceding clause, wherein the structuralcolor has limited iridescence.Clause 66. The article of the preceding clause, wherein the structuralcolor has limited iridescence such that, when each color visible at eachpossible angle of observation is assigned to a single hue selected fromthe group consisting of the primary, secondary and tertiary colors onthe red yellow blue (RYB) color wheel, all of the assigned hues fallinto a single hue group, wherein the single hue group is one of a)green-yellow, yellow, and yellow-orange; b) yellow, yellow-orange andorange; c) yellow-orange, orange, and orange-red; d) orange-red, andred-purple; e) red, red-purple, and purple; f) red-purple, purple, andpurple-blue; g) purple, purple-blue, and blue; h) purple-blue, blue, andblue-green; i) blue, blue-green and green; and j) blue-green, green, andgreen-yellow.Clause 67. The article of any preceding clause, wherein the primer layerconsists essentially of a metal oxide, optionally titanium dioxide orsilicon dioxide, and optionally consists essentially of titaniumdioxide.Clause 68. The article of any preceding clause, wherein the primer layerconsists essentially of a doped metal oxide or a doped metal oxynitrideor both.Clause 69. The article of any preceding clause, wherein the primer layerhas a thickness of about 1 to about 200 micrometers, or optionally ofabout 10 to about 100 micrometers, or optionally of about 10 to about 80micrometers.

It should be noted that ratios, concentrations, amounts, and othernumerical data may be expressed herein in a range format. It is to beunderstood that such a range format is used for convenience and brevity,and thus, should be interpreted in a flexible manner to include not onlythe numerical values explicitly recited as the limits of the range, butalso to include all the individual numerical values or sub-rangesencompassed within that range as if each numerical value and sub-rangeis explicitly recited. To illustrate, a concentration range of “about0.1 percent to about 5 percent” should be interpreted to include notonly the explicitly recited concentration of about 0.1 weight percent toabout 5 weight percent but also include individual concentrations (e.g.,1 percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges(e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4percent) within the indicated range. The term “about” can includetraditional rounding according to significant figures of the numericalvalue. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ toabout ‘y’”.

The term “providing”, such as for “providing an article” and the like,when recited in the claims, is not intended to require any particulardelivery or receipt of the provided item. Rather, the term “providing”is merely used to recite items that will be referred to in subsequentelements of the claim(s), for purposes of clarity and ease ofreadability.

Many variations and modifications may be made to the above-describedaspects. All such modifications and variations are intended to beincluded herein within the scope of this disclosure and protected by thefollowing claims.

We claim:
 1. A method, comprising: disposing a primer layer having apercent transmittance of about 40 percent or less; and disposing anoptical element on a top surface of the primer layer, wherein the primerlayer, and the optical element impart a structural color.
 2. The methodof claim 1, wherein the primer layer further comprises a texturedsurface, and the textured surface of the primer layer, the primer layer,and the optical element impart the structural color.
 3. The method ofclaim 1, wherein the primer layer is on a top surface of a substrate ofan article.
 4. The method of claim 3, wherein the top surface of asubstrate is a textured surface of an article, wherein the primer layeris on the textured surface, and the textured surface of the substrate,the primer layer, and the optical element impart the structural color.5. The method of claim 1, wherein disposing the primer layer comprisingdisposing the primer layer using: digital printing, offset printing, padprinting, screen printing, flexographic printing, or heat transferprinting.
 6. The method of claim 5, wherein the primer layer is a metaloxide or metal oxynitride, wherein the metal oxide or the metaloxynitride is doped.
 7. The method of claim 1, wherein the primer layeris a coating, wherein the coating is a crosslinked coating including amatrix of crosslinked polymers.
 8. The method of claims 7, wherein thematrix of crosslinked polymers include polyurethane polymers, whereinthe polyurethane polymers include polyester polyurethane copolymers. 9.The method of claim 1, wherein the optical element is a multilayerreflector or a multilayer filter.
 10. The method of claim 1, wherein theprimer layer is substantially free of pigments, dyes, and a combinationthereof.
 11. The method of claim 1, wherein the imparted structuralcolor is iridescent.
 12. The method of claim 1, wherein the opticalelement, as disposed onto an article, when measured according to the CIE1976 color space under a given illumination condition at threeobservation angles between −15 degrees and +60 degrees, has a firstcolor measurement at a first angle of observation having coordinates L₁*and a₁* and b₁*, and a second color measurement at a second angle ofobservation having coordinates L₂* and a₂* and b₂*, and a third colormeasurement at a third angle of observation having coordinates L₃* anda₃* and b₃*, wherein the L₁*, L₂*, and L₃* values may be the same ordifferent, wherein the a₁*, a₂*, and a₃* coordinate values may be thesame or different, wherein the b₁*, b₂*, and b₃* coordinate values maybe the same or different, and wherein the range of the combined a₁*, a₂*and a₃* values is less than about 40% of the overall scale of possiblea* values.
 13. A article comprising: a product of the method of claim 1.14. A article comprising: a primer layer having a percent transmittanceof about 40 percent or less and an optical element, wherein the primerlayer, and the optical element impart the structural color.
 15. Thearticle of claim 14, wherein the primer layer is on a top surface of asubstrate of an article, wherein the optical element is on the primerlayer of the substrate.
 16. The article of claim 14, wherein the primerlayer is between a textured surface and the optical element.
 17. Thearticle of claim 14, wherein the textured surface is between the primerlayer and the optical element.
 18. The article of claim 14, wherein thearticle is a yarn.
 19. The article of claim 14, wherein the article isan article of footwear.
 20. The article of claim 14, wherein the articleis a sole of an article of footwear.